WO1994008224A1 - Infrared optical part and measuring instrument - Google Patents
Infrared optical part and measuring instrument Download PDFInfo
- Publication number
- WO1994008224A1 WO1994008224A1 PCT/JP1993/001287 JP9301287W WO9408224A1 WO 1994008224 A1 WO1994008224 A1 WO 1994008224A1 JP 9301287 W JP9301287 W JP 9301287W WO 9408224 A1 WO9408224 A1 WO 9408224A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- prism
- sample
- infrared
- atr
- sample plate
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/55—Specular reflectivity
- G01N21/552—Attenuated total reflection
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2203/00—Processes utilising sub- or super atmospheric pressure
- B01J2203/06—High pressure synthesis
- B01J2203/065—Composition of the material produced
- B01J2203/0655—Diamond
Definitions
- the present invention relates to an optical component mainly used for infrared spectroscopy, and in particular, to an ATR prism capable of measuring an ATR spectrum only by contacting and pressing an object to be measured, and an organic substance.
- the present invention relates to a component such as a sample plate for holding a sample used when measuring a trace impurity or an absorption spectrum of a minute portion with a microscopic infrared spectrometer.
- Table 1 the materials shown in Table 1 have been conventionally used for the prism 1 of this infrared ATR spectroscopic analysis.
- the most suitable material is a natural diamond that has no absorption in the infrared region called IIa type. . ⁇ table 1 ⁇
- diamond has few defects in material, but among diamonds, the type suitable for infrared spectroscopy is absorbed in the infrared region called type IIa. Since this type does not have a yield, this type is only 1 to 2% of the production of natural diamonds, so when it becomes a few millimeters in size such as used for prisms, the production is extremely rare and practically available It was difficult.
- the present invention solves the above-described problems, and when measuring in a place with a bad environment, when measuring the structure itself, or when measuring a sample adhered to clothing, etc., the prism is used as a measurement object. It is an object of the present invention to provide an infrared optical component capable of performing ATR spectroscopic analysis only by contacting and pressing, and a measuring device using the same. Disclosure of the invention
- a compact measuring device By combining an optical mirror or an optical fiber or an optical lens with the above-mentioned synthetic diode, a compact measuring device can be manufactured, and measurement can be performed by directly pressing the sample onto the sample. .
- the prism was shaped to be covered with a minute flat surface that does not reflect the ATR light.
- a lens, prism, or mirror made of a material with the same refractive index as diamond ZnSe, KRS-5, etc.
- diamond ZnSe, KRS-5, etc.
- the diamond ATR prism of the present invention can be used satisfactorily even as a normal prism, and that the spectroscopic analyzer of the present invention can measure not only in the infrared region but also in the visible and ultraviolet regions. It is.
- sample plate for an infrared microscope prepared using the following synthetic diamond is suitable as a sample plate used for infrared spectroscopy for measuring a small amount of impurities and absorption spectra of minute parts. I found that.
- the incident surface of the sample plate for an infrared microscope has a concave hole for holding the measurement sample, and the depth of the hole is 0.011 111 to It is preferable that the surface accuracy at the bottom is 0.5 / zm or less.
- the hole is formed by using an energy beam such as an ion beam or an electron beam.
- a type suitable for infrared spectroscopic analysis is a type having no absorption in the infrared region, which is referred to as a type IIa. Since this type is only 1 to 2% of the output of natural diamond, the output is extremely rare and virtually non-existent when the size of a few millimeters used for a prism is large. Therefore, in the present invention, a synthetic diamond capable of synthesizing a large size is used.
- This synthetic diamond usually uses a metal solvent such as Fe, Ni, and Co. As a result, nitrogen and boron atoms present in the solvent are incorporated into the crystal, causing an absorption peak in the infrared region.
- a metal solvent such as Fe, Ni, and Co.
- diamond is the material with the highest durability and corrosion resistance, and in the present invention, the synthetic diamond is used based on the effect described in 1 of the previous section. I have.
- a sample 2 was processed into a thin piece or a flat plate, brought into contact with the prism surface 3, and pressed with a holder or the like for measurement.
- the present invention has found the following three methods and solved the above-mentioned problems.
- 14 is a prism
- 15 is a sample.
- Incident light 11 incident vertically from below 11 enters the prism 14 with the condensing mirror 12 and condensing lens 13 condensed, and is reflected at the interface with the sample 15 on the prism 14 Then, the light is absorbed and transmitted through the prism 14 to become the measurement light 18, which is guided downward by the condenser lens 16 and the condenser mirror 17 and measured. In this way, a small probe can be created by combining the prism with the mirror and the lens.
- FIG. 3 shows a typical example.
- 24 is a prism
- 25 is a sample
- 26 is a sample stage on which the sample is placed.
- the incident light 21 incident from the lateral direction is guided downward by the turning mirror 22 and is incident on the prism 24 by the condensing mirror 23.
- the prism 24 is lowered and pressed against the sample 25
- the incident light 21 reflects and absorbs at the interface between the prism and the sample
- the measuring light 29 is guided upward by the condensing mirror 27, and changes. Guided laterally by directional mirror ⁇ 8. In this way, even if the prism 24 moves up and down, the measuring light 29 is guided. Measurement is possible without changing the location.
- the incident light 31 passes through the optical fiber 32 and is guided to the prism 33, where it is reflected and absorbed at the interface between the prism 33 and the sample 34, and exits the prism 33 for measurement.
- the light 36 passes through the optical fiber 135 and is guided to a measuring instrument (not shown). Since the probe and the measuring instrument are connected by an optical fiber, the probe can be easily moved to the measuring point and the measurement can be performed easily.
- Diamond has a high refractive index, has a problem that the reflection efficiency of ATR light is reduced due to repeated reflection in the prism.
- the surface where the ATR light is incident or emitted from the prism is covered with a minute surface so as not to cause reflection loss.
- Figure 5 shows a typical example.
- the incident light 41 is condensed by the lens 42 and enters the prism 43. Reflection occurs at the interface between the sample 45 and the prism 43 and is emitted outside the prism.
- the prism 43 is covered with a minute surface 44.
- the emitted measurement light 47 is deflected by the mirror 46 and sent to the measurement system.
- a diamond cannot have a curved surface due to poor workability. Also expensive Therefore, there is a disadvantage that the larger the anvil, the higher the price. For this reason, a substance (for example, ZuSe, KRS5, etc.) having a refractive index substantially equal to that of the diamond is processed in advance, and incident and condensed light loss are prevented by contacting and combining with the diamond. Also, by replacing a part of the diamond with these substances, a large prism is obtained and the measurement accuracy is improved.
- Figure 6 shows an example.
- the incident light 51 is incident on a diamond 53 subjected to a curved surface processing and the like and a substance 53 having an equal refractive index through a converging mirror 52, and is incident on the diamond prism 54 without reflection. It is totally reflected at the interface with the sample 55 and is emitted out of the diamond and the material 53 with the same refractive index. At this time, since the diamond and the equirefractive index material 53 are processed into a curved surface, there is almost no reflection loss. The emitted measuring light 57 is collected by the mirror 56.
- the sample plate Since the synthetic diamond is used for the sample plate for an infrared microscope of the present invention, the sample plate has high strength and poor reactivity with various samples, so that the sample plate is excellent.
- any of the materials shown in Table 1 except for diamond had problems in chemical stability, and the sample preparation method There were many restrictions in various aspects such as the observation method.
- this sample plate Usually, it is in the form of a plate, but the parallelism between the upper and lower surfaces is especially important. For example, when a sample is placed in the sample insertion portion 62 of the sample plate 61 for the infrared microscope shown in FIG. 7 and observed with the infrared microscope, the incident surface 63 and the transmission surface 64 are parallel. The degree must be kept within one minute.
- the sample plate 61 for an infrared microscope of the present invention shown in FIG. 7 has a size of 1 to 5 mm ⁇ , usually about 2 to 3 mm, and a sample having a concave hole on the incident surface 63.
- An entry 62 is formed.
- the diameter of the sample introduction part 62 is preferably 0.5 mm mm ⁇ and the depth is preferably in the range of about 0.5 to 100.
- the surface accuracy at the bottom of the hole is preferably 0.5 m or less.
- sample inlet 62 When performing infrared spectroscopy analysis, fill the sample inlet 62 with a sample for measurement, place a diamond disk without recesses on top of it and fix it, and irradiate infrared light from the incident surface 63 side. The absorption in the infrared region of the transmitted light transmitted through the sample inlet is measured.
- FIG. 1 is a front view showing a measurement method using a general ATR prism.
- FIG. 2 is a front view showing the ATR measuring apparatus according to the invention of the present invention in which measurement is performed with the prism fixed downward.
- FIG. 3 is a front view showing an ATR measuring apparatus of the present invention in which a prism is arranged above a sample and measured by making a downward contact.
- FIG. 4 is a front view showing an ATR measuring apparatus of the present invention in which a probe and a measuring instrument are connected by an optical fiber.
- FIG. 5 is a front view showing a measuring apparatus using a prism covered with a minute plane according to the present invention.
- FIG. 6 is a front view showing a measuring apparatus using a prism in which a diamond and a substance having an equal refractive index are combined according to the present invention.
- FIG. 7 is a material plate for an infrared microscope according to the present invention, wherein (A) is a perspective view and (B) is a central longitudinal sectional view.
- High-purity single crystals were synthesized using the temperature difference method in a pressure and temperature range where diamonds were stable.
- the solvent used in the synthesis was an Fe—40Co alloy.
- A1Ti alloy was added to remove nitrogen.
- a solvent metal was prepared using raw materials with different purity and used for synthesis.
- the synthesized crystal was processed as shown in Fig. 2 and ATR spectroscopy was performed. [Table 2]
- the prism used in Experiment No. 1 of Example 1 was reworked into the shape indicated by 24 in FIG.
- the prism 24 was set as shown in FIG. 3, the incident light 21 was changed in direction by the turning mirror 22, and was put into the prism 24 by the condensing mirror 23. Lower the set prism 24, and press it against the sample 25 on the sample stage 26. I was
- the incident light 21 repeats total reflection at the interface between the prism 24 and the sample 25 to cause absorption, and radiates in a direction opposite to the incidence.
- the measurement light 29 transmitted through the prism 24 is condensed by the Cassegrain mirror 27 and introduced into the measurement system by the deflection mirror 28.
- a hemispherical KRS-5 lens 53 was stuck on a diamond disk 54. These were fixed and pressed onto the sample 55 to measure ATR.
- the incident light 51 was made incident from the right vertical direction, collected by the mirror 52, and introduced into the hemispherical lens 53 (KRS-5).
- the introduced light did not reflect at the interface with the diamond plate 54, but was reflected at the interface between the sample 55 and the diamond plate 54 to cause absorption.
- the reflected light was emitted to the outside without any reflection loss on the surface of the hemispherical 53 lens.
- the emitted measuring light 57 was introduced into the measuring system by a focusing mirror 56. With the method described above, the impurities mixed in the polyethylene film were successfully fixed. When the measurement was performed with the hemispherical 53 lens removed, the intensity of the measuring light 57 was low, and impurities could not be fixed.
- the diamond single crystal obtained in Example 1 was processed into a disk having a diameter of 2 mm and a thickness of l mm.
- the parallelism between the upper plane 63 and the lower plane 64 was set to be less than 1 second.
- a counterbore hole having a diameter of 0.5 mm0 and a depth of 7 t / m was opened in the center to prepare a sample plate 61 for microscopic infrared spectroscopic analysis as shown in FIG.
- the surface roughness of the bottom of the hole, which is the sample inlet 62, is 0.3111 in Rmax. there were.
- the same disk-shaped sample plate as above without a counterbore in the center was prepared.
- aqueous solution in which organic matter was dissolved was filled into the counterbore 62, and a sample plate without a counterbore was placed on the measurement optical path to prevent the sample from rising due to surface tension. .
- a sample plate according to the present invention enables infrared spectroscopy to be performed on a sample dissolved in an acid or alkaline solution, which could not be measured because the sample plate was eroded in the past. Was.
- a prism having excellent durability can be provided in infrared spectroscopy using the ATR prism of the present invention.
- it became possible to measure the sample by processing it into a flake shape and pressing it directly without bonding it to the prism with a holder or the like.
- the sample plate for an infrared microscope of the present invention has poor reactivity with various samples, is optimal as a sample plate, and has high strength and a large number of service times compared to a conventional sample plate. Improved.
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP93919640A EP0624785B1 (en) | 1992-10-07 | 1993-09-10 | Infrared optical part and measuring instrument |
DE69322256T DE69322256T2 (de) | 1992-10-07 | 1993-09-10 | Optisches element für den infrarotbereich und messvorrichtung |
US08/244,635 US5569921A (en) | 1992-10-07 | 1993-09-19 | Infrared optical part and measuring instrument |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4/296326 | 1992-10-07 | ||
JP29632692 | 1992-10-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994008224A1 true WO1994008224A1 (en) | 1994-04-14 |
Family
ID=17832092
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1993/001287 WO1994008224A1 (en) | 1992-10-07 | 1993-09-10 | Infrared optical part and measuring instrument |
Country Status (5)
Country | Link |
---|---|
US (1) | US5569921A (ja) |
EP (1) | EP0624785B1 (ja) |
DE (1) | DE69322256T2 (ja) |
WO (1) | WO1994008224A1 (ja) |
ZA (1) | ZA936715B (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0801736A4 (en) * | 1994-05-13 | 1998-07-29 | Applied Systems Inc | OPTICAL DETECTION BY CRYSTAL SET DETECTION POINT |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5706135A (en) * | 1995-10-03 | 1998-01-06 | General Electric Company | Diamond optical plate beamsplitter |
US5818046A (en) * | 1996-08-30 | 1998-10-06 | Rizvi; Syed A. | Mid-infrared analysis system |
US5945674A (en) * | 1997-07-30 | 1999-08-31 | Vysis, Inc. | Method of identifying cellular types in a biological sample supported on an absorptive substrate by infrared spectroscopy |
AU4160099A (en) * | 1998-06-18 | 2000-01-05 | Drukker International B.V. | A spectroscopic analyzing arrangement |
GB9908170D0 (en) * | 1999-04-09 | 1999-06-02 | Central Research Lab Ltd | System and method for analysing a material |
DE10028653B4 (de) * | 2000-06-09 | 2006-04-27 | Gesellschaft zur Förderung der Spektrochemie und angewandten Spektroskopie e.V. | Messsonde für Infrarot-Spektroskopie |
GB0021502D0 (en) * | 2000-09-01 | 2000-10-18 | Central Research Lab Ltd | An attenuated total reflectance sensing head |
AT410322B (de) * | 2001-04-05 | 2003-03-25 | Lendl Bernhard Dipl Ing Dr Ins | Verfahren zur prozessüberwachung von biotechnologischen prozessen |
US7145147B1 (en) * | 2005-06-30 | 2006-12-05 | The Boeing Company | Apparatus and methods of determining chemical properties of a resin-based material using infrared absorbance |
DE102005052223B3 (de) * | 2005-10-30 | 2007-06-14 | Küpper, Lukas, Dipl.-Phys. | Temperaturfeste Infrarot-Messsonde |
US8203700B2 (en) * | 2007-05-21 | 2012-06-19 | Ahura Scientific Inc. | Supporting remote analysis |
US7675611B2 (en) | 2007-05-21 | 2010-03-09 | Ahura Scientific Inc. | Handheld infrared and Raman measurement devices and methods |
KR101017796B1 (ko) * | 2009-01-22 | 2011-02-28 | 한국과학기술원 | 접촉형 테라헤르츠 시간 도메인 분광 장치 |
DE102010010948A1 (de) * | 2010-03-10 | 2011-09-15 | Karl Storz Gmbh & Co. Kg | Schwenkprismenendoskop |
DE102011085615A1 (de) * | 2010-11-09 | 2012-07-12 | Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG | ATR Sonde zur Untersuchung eines Mediums mittels einer optischen Strahlung |
CN102323218A (zh) * | 2011-05-26 | 2012-01-18 | 浙江大学 | 基于光谱技术的物料实时检测监控装置 |
DE102015122995A1 (de) * | 2015-12-30 | 2017-07-06 | Blue Ocean Nova AG | Vorrichtung zur Analyse von einem sich in einem Produktraum befindenden zu analysierenden Gut |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61281946A (ja) * | 1985-06-07 | 1986-12-12 | Hitachi Ltd | 全反射赤外吸収スペクトル測定法 |
JPS622138A (ja) * | 1985-06-25 | 1987-01-08 | ザ ダウ ケミカル カンパニ− | 流体媒質の光吸収を測定する方法と装置 |
JPH04116452A (ja) * | 1990-09-07 | 1992-04-16 | Canon Inc | 顕微赤外atr測定装置 |
JPH04178539A (ja) * | 1990-11-14 | 1992-06-25 | Hitachi Ltd | 減衰全反射プリズムセル |
JPH04234001A (ja) * | 1990-07-09 | 1992-08-21 | General Electric Co <Ge> | 同位体純度の高い単結晶ダイヤモンドから成る放射線抵抗性の光学製品 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH064841B2 (ja) * | 1989-06-28 | 1994-01-19 | 日本鋼管株式会社 | 赤外線散乱剤の製造方法 |
JPH04138340A (ja) * | 1990-09-29 | 1992-05-12 | Shimadzu Corp | 赤外スペクトル測定ヘッド及び測定装置 |
US6129900A (en) * | 1991-02-15 | 2000-10-10 | Sumitomo Electric Industries, Ltd. | Process for the synthesis of diamond |
IE74163B1 (en) * | 1991-03-14 | 1997-07-02 | Sumitomo Electric Industries | Infrared optical part and method of making the same |
US5200609A (en) * | 1991-08-27 | 1993-04-06 | Sting Donald W | Radiant energy spectroscopy system with diamond internal reflection element |
-
1993
- 1993-09-10 WO PCT/JP1993/001287 patent/WO1994008224A1/ja active IP Right Grant
- 1993-09-10 EP EP93919640A patent/EP0624785B1/en not_active Expired - Lifetime
- 1993-09-10 ZA ZA936715A patent/ZA936715B/xx unknown
- 1993-09-10 DE DE69322256T patent/DE69322256T2/de not_active Expired - Lifetime
- 1993-09-19 US US08/244,635 patent/US5569921A/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61281946A (ja) * | 1985-06-07 | 1986-12-12 | Hitachi Ltd | 全反射赤外吸収スペクトル測定法 |
JPS622138A (ja) * | 1985-06-25 | 1987-01-08 | ザ ダウ ケミカル カンパニ− | 流体媒質の光吸収を測定する方法と装置 |
JPH04234001A (ja) * | 1990-07-09 | 1992-08-21 | General Electric Co <Ge> | 同位体純度の高い単結晶ダイヤモンドから成る放射線抵抗性の光学製品 |
JPH04116452A (ja) * | 1990-09-07 | 1992-04-16 | Canon Inc | 顕微赤外atr測定装置 |
JPH04178539A (ja) * | 1990-11-14 | 1992-06-25 | Hitachi Ltd | 減衰全反射プリズムセル |
Non-Patent Citations (1)
Title |
---|
See also references of EP0624785A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0801736A4 (en) * | 1994-05-13 | 1998-07-29 | Applied Systems Inc | OPTICAL DETECTION BY CRYSTAL SET DETECTION POINT |
Also Published As
Publication number | Publication date |
---|---|
EP0624785B1 (en) | 1998-11-25 |
ZA936715B (en) | 1994-04-13 |
US5569921A (en) | 1996-10-29 |
DE69322256D1 (de) | 1999-01-07 |
DE69322256T2 (de) | 1999-05-27 |
EP0624785A4 (en) | 1995-02-22 |
EP0624785A1 (en) | 1994-11-17 |
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