WO2013058364A1 - 高分子薄膜構造体及び有機膜の深さ方向の分析方法 - Google Patents

高分子薄膜構造体及び有機膜の深さ方向の分析方法 Download PDF

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Publication number
WO2013058364A1
WO2013058364A1 PCT/JP2012/077109 JP2012077109W WO2013058364A1 WO 2013058364 A1 WO2013058364 A1 WO 2013058364A1 JP 2012077109 W JP2012077109 W JP 2012077109W WO 2013058364 A1 WO2013058364 A1 WO 2013058364A1
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Prior art keywords
thin film
polymer
depth direction
film structure
polymer thin
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PCT/JP2012/077109
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English (en)
French (fr)
Japanese (ja)
Inventor
美那 松尾
雄貴 野原
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日産化学工業株式会社
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Priority to JP2013539703A priority Critical patent/JP6281283B2/ja
Priority to KR1020147013036A priority patent/KR102006348B1/ko
Publication of WO2013058364A1 publication Critical patent/WO2013058364A1/ja

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/225—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion
    • G01N23/2255—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion using incident ion beams, e.g. proton beams
    • G01N23/2258—Measuring secondary ion emission, e.g. secondary ion mass spectrometry [SIMS]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns
    • H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
    • H01J49/142—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers using a solid target which is not previously vapourised
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/60—Specific applications or type of materials
    • G01N2223/61—Specific applications or type of materials thin films, coatings
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/60—Specific applications or type of materials
    • G01N2223/633—Specific applications or type of materials thickness, density, surface weight (unit area)

Definitions

  • Functional properties of organic thin films and polymer thin films vary greatly depending on the material surface, the composition at the substrate interface, the state of layer separation, and the like.
  • functional organic materials such as liquid crystal alignment films, antireflection films for semiconductor lithography, and organic EL materials
  • additives such as additives that impart properties such as alignment characteristics, lithography characteristics, and surface liquid repellency are provided on the outermost surface of the material.
  • the composition and internal distribution state are greatly involved in the expression of the function. Therefore, it is indispensable for the development of functional organic materials to evaluate the distribution of such substances in the depth direction from the material surface.
  • each ion beam can be individually optimized by using a dual beam method in which a primary ion beam for measurement and a sputter ion beam for sputtering are used together. Therefore, the depth is excellent in horizontal resolution and mass resolution by TOF-SIMS.
  • Direction analysis became possible. However, in this case, since the molecular structure is destroyed by sputtering as in D-SIMS, there is a problem that it is difficult to perform measurement while maintaining the original structure. Further, in the depth direction analysis by TOF-SIMS, there is a transition region where the secondary ion yield is not stable immediately after the start of etching by sputter ions. Therefore, it is very difficult to evaluate the distribution state of the target substance near the surface of the material. In addition, as the sample is easily charged, the width of the transition region becomes wider, which makes it difficult to analyze the depth direction in the vicinity of the surface of the organic film.
  • the present invention has been made in view of the above problems, and provides an analysis method for simply and accurately analyzing a distribution state of a component in a depth direction and a layer separation structure in a polymer thin film structure. Objective. It is another object of the present invention to provide a method for simply and accurately analyzing the distribution state of trace components unevenly distributed near the surface of an organic film.
  • the present inventors have found that at least one polymer compound is stable isotope even in a polymer thin film structure containing two or more polymer compounds. Sputtering a polymer thin film structure containing a labeled polymer compound along the depth direction thereof with sputter ions and time-of-flight secondary ion mass spectrometry. The process of obtaining the mass spectrum of the secondary ion is repeated to obtain the depth profile of the fragment containing the stable isotope, thereby simplifying the distribution state and the layer separation state of the constituent components in the polymer thin film structure. And found that it can be analyzed accurately.
  • the polymer thin film structure analysis method of the present invention it is possible to easily and accurately analyze the distribution state of the components in the depth direction and the layer separation structure in the polymer thin film structure.
  • the analysis method of the present invention can also be applied to a thin polymer thin film structure. Moreover, it is suitable as a method for analyzing a distribution state of a component in a depth direction and a layer separation structure in a structure including a polymer blend thin film obtained by blending two or more kinds of polymers.
  • the substance to be analyzed has a chemical bond state or an element different from other components, and an element that is such a discrimination factor is added.
  • the thickness of the polymer thin film structure to be analyzed is 10 to 500 nm, which is difficult to analyze by other methods. Analysis is possible if the thickness is up to ⁇ m. According to the analysis method of the present invention, it is possible to analyze even when the polymer thin film structure to be analyzed has a particularly thin thickness of 10 to 200 nm, 10 to 150 nm, and further 10 to 100 nm. .
  • the introduction of the above stable isotope is not an atom that can be lost due to polymerization reaction, condensation reaction, etc. among the constituent atoms of the analysis target substance, but forms an atom that reliably remains in the polymer skeleton to be formed, for example, an imide bond in polyimide It is preferable that the nitrogen atom and the carbon of the main skeleton are the targets for substitution of stable isotopes.
  • a structure containing a polymer compound labeled with a stable isotope is sputtered along the depth direction with sputter ions, and a secondary ion containing the stable isotopes is obtained by TOF-SIMS.
  • a depth profile of the fragment containing the stable isotope is obtained by repeating the step of acquiring a mass spectrum.
  • the carbon coating layer When the carbon coating layer is formed by vacuum deposition, it can be formed using a carbon coater or a vacuum deposition apparatus.
  • a carbon coater a non-conductive sample is used for pretreatment of a sample when performing observation or analysis using a charged particle beam device such as a scanning electron microscope (SEM) or an electron probe microanalyzer (EPMA). Similar ones can be used. Therefore, it is not a technique that requires special pre-preparation or skill, and pre-processing can be easily performed in a short time.
  • SEM scanning electron microscope
  • EPMA electron probe microanalyzer
  • the thickness of the carbon coating layer only needs to correspond to the thickness of the transition region where the yield of secondary ions is unstable in the early stage of analysis. Specifically, 5 nm or more is preferable.
  • the upper limit of the thickness is not particularly defined, but it is preferably as thin as possible in order to shorten the measurement time and suppress thermal damage due to the formation of the carbon coating layer.
  • the thickness is preferably 50 nm or less, more preferably 40 nm or less, still more preferably 20 nm or less, and particularly preferably 10 nm or less. However, this is not the case when the sputtering rate by TOF-SIMS measurement is fast.
  • the carbon source for forming the carbon coating layer is not particularly limited, and examples thereof include graphite (graphite), carbon black, activated carbon, and the like, among which graphite (graphite) is preferable.
  • the shape is not particularly limited, and various shapes such as powder, granule, fiber, and core can be adopted. Of these, fiber and core are preferable.
  • the diameter of the fibrous and core carbon is preferably 5 to 10 ⁇ m.
  • the purity of carbon is preferably 99.9% or more, and more preferably 99.99% or more.
  • CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • FIG. 1 is a cross-sectional view of the produced two-layer separated structure model sample.
  • the thin film forming composition B was applied onto the ITO substrate 3 by a spin coating method, and a polymer B layer 2 was formed according to the following film forming conditions.
  • the thin film forming composition A is applied onto the polymer B layer 2 by a spin coating method, and the polymer A layer 1 is formed according to the following film formation conditions.
  • a model of a two-layer separation structure for Example 1 A sample was prepared.
  • a two-layer separated structure model sample for Comparative Example 1 was prepared in the same manner as the above method except that the polymer A ′ layer 1 was formed using the thin film forming composition A ′.
  • Film forming conditions First layer (polymer B layer) pre-drying 70 ° C., 70 sec, baking 250 ° C., 10 min, film thickness 120 nm, Second layer (Polymer A (A ′) layer) Firing at 250 ° C., 10 min, film thickness of 120 nm (total film thickness of 240 nm)
  • the measured value is plotted with the sputter time on the horizontal axis and the secondary ion detection intensity at the sputter time on the vertical axis, and the depth profile is obtained by graphing the relationship between the sputter time and the secondary ion intensity.
  • the measurement conditions for TOF-SIMS are as follows.
  • Primary ion 25 keV Bi 3 2+ , 0.2 pA (pulse current value), random scan mode
  • Primary ion scan range 100 ⁇ m ⁇ 100 ⁇ m
  • Primary ion pulse frequency 10 kHz (100 ⁇ s / shot)
  • Primary ion beam diameter about 5 ⁇ m
  • Secondary ion detection mode negative Number of scans: 1scan / cycle (A flat gun is used for charging correction)
  • Film forming conditions First layer (polymer B layer) pre-drying 70 ° C., 70 sec, baking 250 ° C., 10 min, film thickness 60 nm, Second layer (polymer C layer) calcination 250 ° C., 10 min, film thickness 60 nm (Total film thickness 120 nm)
  • Primary ion 25 keV Bi 3 2+ , 0.2 pA (pulse current value), random scan mode
  • Primary ion scan range 60 ⁇ m ⁇ 60 ⁇ m
  • Primary ion pulse frequency 10 kHz (100 ⁇ s / shot)
  • Primary ion beam diameter about 5 ⁇ m
  • Secondary ion detection mode negative Number of scans: 1scan / cycle (A flat gun and oxygen gas (vacuum level: 1.0 ⁇ 10 -6 mbar) are used for charging correction)
  • Sputter ion Cs + (20 nA, 500 eV)
  • Sputtering area 200 ⁇ m ⁇ 200 ⁇ m
  • the result of the model sample using the polymer C which is Example 2 is shown in FIG.
  • the boundary between the polymer C layer and the polymer B layer was visualized even in the case of a model sample having a two-layer separation structure using a polymer C into which a stable isotope was introduced, and the two-layer separation structure could be analyzed.
  • the method of the present invention is also suitable for analyzing the layer separation structure of an extremely thin film structure having a film thickness of about 120 nm.
  • Primary ion 25 keV Bi 3 2+ , 0.2 pA (pulse current value), random scan mode
  • Primary ion scan range 50 ⁇ m ⁇ 50 ⁇ m
  • Primary ion pulse frequency 10 kHz (100 ⁇ s / shot)
  • Primary ion beam diameter about 5 ⁇ m
  • Secondary ion detection mode negative Number of scans: 1scan / cycle (A flat gun is used for charging correction)
  • the horizontal axis represents the depth from the sample surface
  • the vertical axis represents the concentration of each ion.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
PCT/JP2012/077109 2011-10-21 2012-10-19 高分子薄膜構造体及び有機膜の深さ方向の分析方法 WO2013058364A1 (ja)

Priority Applications (2)

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JP2013539703A JP6281283B2 (ja) 2011-10-21 2012-10-19 高分子薄膜構造体及び有機膜の深さ方向の分析方法
KR1020147013036A KR102006348B1 (ko) 2011-10-21 2012-10-19 고분자 박막 구조체 및 유기막의 깊이 방향의 분석 방법

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021534260A (ja) * 2018-06-25 2021-12-09 インスティテュート ナシオナル デ テクニカ アエロスパシアルInstituto Nacional De Tecnica Aeroespacial 分解検出のための同位体標識付けされた材料
CN115235861A (zh) * 2022-08-25 2022-10-25 胜科纳米(苏州)股份有限公司 一种用于飞行时间二次离子质谱分析的超薄有机膜层的制样及分析方法

Citations (2)

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Publication number Priority date Publication date Assignee Title
JPH06249805A (ja) * 1993-03-01 1994-09-09 Nissin Electric Co Ltd 表面分析方法
JP2004219261A (ja) * 2003-01-15 2004-08-05 Fuji Photo Film Co Ltd 薄膜の解析方法

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EP1688246B1 (en) * 2003-11-27 2015-09-16 Mitsubishi Plastics, Inc. Gas barrier film
JP3790539B2 (ja) * 2003-11-27 2006-06-28 三菱樹脂株式会社 ガスバリア性フィルム
JP5142580B2 (ja) * 2006-06-29 2013-02-13 キヤノン株式会社 表面解析方法および表面解析装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06249805A (ja) * 1993-03-01 1994-09-09 Nissin Electric Co Ltd 表面分析方法
JP2004219261A (ja) * 2003-01-15 2004-08-05 Fuji Photo Film Co Ltd 薄膜の解析方法

Non-Patent Citations (2)

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Title
HARTON S E ET AL.: "Carbon-13 Labeled Polymers: An Alternative Tracer for Depth Profiling of Polymer Films and Multilayers Using Secondary Ion Mass Spectrometry", ANALYTICAL CHEMISTRY, vol. 78, no. 10, 15 May 2006 (2006-05-15), pages 3452 - 3460 *
HARTON S E ET AL.: "Carbon-13 Labeling for Quantitative Analysis of Molecular Movement in Heterogeneous Organic Materials Using Secondary Ion Mass Spectrometry", ANALYTICAL CHEMISTRY, vol. 79, no. 14, 15 July 2007 (2007-07-15), pages 5358 - 5363 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021534260A (ja) * 2018-06-25 2021-12-09 インスティテュート ナシオナル デ テクニカ アエロスパシアルInstituto Nacional De Tecnica Aeroespacial 分解検出のための同位体標識付けされた材料
CN115235861A (zh) * 2022-08-25 2022-10-25 胜科纳米(苏州)股份有限公司 一种用于飞行时间二次离子质谱分析的超薄有机膜层的制样及分析方法

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KR102006348B1 (ko) 2019-08-01
KR20140090207A (ko) 2014-07-16
JP6281283B2 (ja) 2018-02-21
TW201331579A (zh) 2013-08-01
JPWO2013058364A1 (ja) 2015-04-02
TWI640769B (zh) 2018-11-11

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