WO2023037564A1 - Analysis liquid recovery method - Google Patents
Analysis liquid recovery method Download PDFInfo
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- WO2023037564A1 WO2023037564A1 PCT/JP2021/037835 JP2021037835W WO2023037564A1 WO 2023037564 A1 WO2023037564 A1 WO 2023037564A1 JP 2021037835 W JP2021037835 W JP 2021037835W WO 2023037564 A1 WO2023037564 A1 WO 2023037564A1
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- Prior art keywords
- analysis
- substrate
- analysis liquid
- nozzle
- outer tube
- Prior art date
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- 238000004458 analytical method Methods 0.000 title claims abstract description 97
- 239000007788 liquid Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000011084 recovery Methods 0.000 title abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 86
- 238000010408 sweeping Methods 0.000 claims abstract description 9
- 230000005660 hydrophilic surface Effects 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 11
- 239000012498 ultrapure water Substances 0.000 description 11
- 150000001450 anions Chemical class 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 5
- -1 chlorine ions Chemical class 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N35/00—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
- G01N35/10—Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices
Definitions
- the present invention relates to a method for recovering an analysis liquid when analyzing an analysis target such as trace metals contained in a substrate or anions present on the substrate surface using a substrate analysis nozzle.
- impurities such as trace metals and organic substances mixed in the substrate during the manufacturing process and anions present on the substrate surface are recovered and analyzed using a trace amount of analysis liquid.
- a minute amount of analysis liquid is discharged onto the surface of a substrate such as a silicon wafer, the substrate surface is swept with the discharged analysis liquid to recover impurities, and the recovered analysis liquid is analyzed by an inductively coupled plasma mass spectrometer (ICP-MS). MS), ion chromatography, or the like.
- ICP-MS inductively coupled plasma mass spectrometer
- MS ion chromatography
- a substrate analysis nozzle is used that ejects an analysis liquid from its tip onto a substrate, sweeps the surface of the substrate with the ejected analysis liquid, and then sucks the analysis liquid.
- the substrate analysis nozzle discharges the analysis liquid from the tip onto the substrate, sweeps the substrate surface with the discharged analysis liquid, and then sucks the analysis liquid.
- an outer tube arranged on the outer periphery of the nozzle body so as to surround the sweeping analysis liquid for example, Patent Document 1.
- the double-tube structure substrate analysis nozzle disclosed in Patent Document 1 is capable of sweeping the substrate surface in a short period of time, and has the characteristic that the analysis liquid is less likely to fall off during the sweep.
- the substrate analysis nozzle 1 is composed of a double tube consisting of a nozzle body 10 and an outer tube 20.
- the nozzle body 10 is connected to a syringe pump 30 by a tube. It is possible to discharge from.
- the outer tube 20 is provided with a suction means 21 connected to a pump (not shown) so that the space between the nozzle body 10 and the outer tube 20 becomes a reduced pressure atmosphere.
- the analysis liquid D held at the tip of the nozzle body 10 sweeps the surface of the substrate to be analyzed. During the sweep, the atmosphere between the nozzle body 10 and the outer tube 20 is reduced to prevent the analysis liquid held at the tip of the nozzle body 10 from falling off.
- the present invention provides a method for recovering an analysis liquid that can recover an analysis liquid at a high recovery rate when analyzing a substrate having a highly hydrophilic surface using a substrate analysis nozzle with a double-tube structure. intended to provide
- the present invention provides a nozzle body capable of discharging and sucking an analysis liquid, and an outer tube arranged around the nozzle body so as to surround the analysis liquid held at the tip of the nozzle body and sweeping the substrate.
- a method for recovering an analytical liquid comprising: using a substrate analyzing nozzle equipped with a suction means for creating a reduced pressure atmosphere between a nozzle body and an outer tube; When sweeping the substrate surface with the liquid, the height position of the tip of the nozzle body and the outer tube is the same. It is characterized by recovering the analytical solution.
- the analysis solution was swept and collected according to the following procedure.
- the tip of the substrate analysis nozzle (the tip of the nozzle body and the tip of the outer tube are at the same height position) is moved to the vicinity of the substrate surface.
- the analysis liquid is discharged from the tip of the nozzle body.
- the space between the nozzle main body and the outer tube is in a reduced pressure atmosphere, the analysis liquid is held at the tip side of the substrate analysis nozzle without leaking from the outer tube.
- the substrate surface is swept with the analysis liquid.
- the analysis liquid is collected by sucking it from the tip of the nozzle body.
- the tip of the substrate analysis nozzle is arranged near the surface of the substrate, that is, the tip of the nozzle body and the tip of the outer tube are at the same height position.
- the surface tension between the outer tube and the substrate tends to hold the analysis solution in the gap between the tip of the outer tube and the substrate surface. becomes stronger, cracking occurs when the analysis liquid is recovered at the tip of the nozzle body, and the analysis liquid adhering to the outer tube cannot be recovered.
- the tip of the outer tube is separated from the substrate surface after the sweep is completed.
- the analysis liquid is efficiently collected by the nozzle main body. Therefore, according to the present invention, the analysis liquid can be recovered at a high recovery rate, and the amount of the analysis liquid remaining on the substrate surface after recovery can be reduced.
- the structure of the substrate analysis nozzle for keeping the tip of the outer tube away from the substrate surface is not particularly limited.
- a structure in which the nozzle body and the outer tube are detachable or a structure in which the outer tube can move up and down with respect to the nozzle body can be adopted.
- the present invention is suitable for highly hydrophilic substrate surfaces, it can also be applied to hydrophobic substrate surfaces.
- the analysis liquid is not particularly limited, and a mixed liquid of hydrogen fluoride and hydrogen peroxide, aqua regia, ultrapure water, or the like can be used.
- the present invention is particularly effective when analyzing a highly hydrophilic substrate surface using ultrapure water.
- the analytical liquid recovery method of the present invention is capable of recovering the analytical liquid at a high recovery rate even on a highly hydrophilic substrate surface, and the analytical liquid remaining on the substrate surface after recovery can be eliminated. can be reduced.
- FIG. 3 is a cross-sectional view of a conventional double-tube substrate analysis nozzle.
- FIG. 2 is a cross-sectional view of a double-tube substrate analysis nozzle of the present invention. Sectional drawing of collection
- FIG. 2 shows a cross-sectional view of the substrate analysis nozzle of this embodiment.
- the substrate analysis nozzle 1 shown in FIG. 2 is composed of a double tube consisting of a nozzle body 10 and an outer tube 20.
- the outer tube 20 is detachable from the nozzle body 10, and has a ring shape. It is attached to the nozzle body 10 via a magnet 22 .
- the nozzle body 10 is connected to the syringe pump 30 by a tube, so that the analysis liquid D can be discharged to the tip side.
- the outer tube 10 is provided with a suction means 21 connected to a pump (not shown) so that the space between the nozzle body 10 and the outer tube 20 becomes a reduced pressure atmosphere.
- the nozzle sweeping operation can be arbitrarily performed on the entire surface of the substrate W by, for example, moving the nozzle from the inside to the outside while rotating the substrate (wafer W).
- the nozzle body 10 and the outer tube 20 are made of stainless steel or fluororesin.
- a nozzle body 10 with a tip diameter of 0.8 to 2 mm can be used, and an outer tube with a diameter of 5 mm to 40 mm can be used.
- the diameter of the outer tube is appropriately determined in consideration of the type of analysis liquid.
- An 8-inch SiC wafer was used as the substrate to be analyzed, and ultrapure water was used as the analysis liquid in order to analyze the anions on the surface of this substrate, and the recovery rate of the analysis liquid was investigated.
- the diameter of the nozzle body was 1 mm, and the diameter of the outer tube was 20 mm.
- the recovery rate of the analytical solution was determined according to the following procedure. First, a predetermined amount (1000 ⁇ L) of ultrapure water is aspirated by the nozzle body alone, and then the outer tube is attached to the nozzle body so that the tips of the nozzle body and the outer tube are at the same height position, and the analysis target is The substrate analysis nozzle was lowered from above the substrate so that the tip of the substrate analysis nozzle was positioned 0.5 mm above the substrate surface. By this operation, the tip of the nozzle main body and the tip of the outer tube are positioned at the same height above the substrate surface by 0.5 mm. Thereafter, 1000 ⁇ L of ultrapure water was discharged from the nozzle body onto the substrate surface to sweep the substrate surface.
- the space between the nozzle main body and the outer tube was made to have a reduced pressure atmosphere by the suction means.
- all the ultrapure water is discharged onto the substrate surface, and the substrate analysis nozzle is once raised.
- an analysis liquid can be recovered at a high recovery rate even with a highly hydrophilic substrate.
- ultrapure water when ultrapure water is used as the analysis liquid, ultrapure water can be recovered at a high recovery rate. It is possible to improve the analysis accuracy of anion analysis.
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The objective of the present invention is to provide an analysis liquid recovery method with which it is possible to collect an analysis liquid with a high recovery rate, even in the case of a highly hydrophilic substrate. The present invention provides an analysis liquid recovery method for employing a nozzle main body to recover an analysis liquid that has swept a substrate surface, using a substrate analysis nozzle which comprises the nozzle main body, capable of discharging and sucking the analysis liquid, and an outer tube disposed at an outer periphery of the nozzle main body so as to enclose the analysis liquid that is held at a tip end of the nozzle main body and that sweeps the substrate, the substrate analysis nozzle being provided with a suction means for creating a reduced-pressure atmosphere between the nozzle main body and the outer tube, and the analysis liquid recovery method being characterized in that, when the substrate surface is being swept by the analysis liquid, the nozzle main body and the outer tube are disposed such that height positions of tip ends thereof are the same, and after the sweeping is complete, the analysis liquid is recovered by means of the nozzle main body in a state in which the tip end of the outer tube is separated from the substrate surface.
Description
本発明は、基板に含まれる微量金属や基板表面に存在する陰イオン等の分析対象を、基板分析用ノズルを用いて分析する際の分析液の回収方法に関する。
The present invention relates to a method for recovering an analysis liquid when analyzing an analysis target such as trace metals contained in a substrate or anions present on the substrate surface using a substrate analysis nozzle.
半導体ウェーハ等の基板においては、製造工程等により基板に混入した微量金属や有機物質、基板表面に存在する陰イオン等の不純物を、微量の分析液により回収して分析することが行われている。具体的には、シリコンウェーハ等の基板表面に、微量の分析液を吐出し、吐出した分析液で基板表面を掃引し不純物を回収し、回収した分析液を誘導結合プラズマ質量分析装置（ＩＣＰ－ＭＳ）やイオンクロマトグラフィーなどにより分析する。そして、このような分析には、先端から基板上に分析液を吐出し、吐出した分析液で基板表面を掃引した後に分析液を吸引するようになっている基板分析用ノズルが用いられる。
In substrates such as semiconductor wafers, impurities such as trace metals and organic substances mixed in the substrate during the manufacturing process and anions present on the substrate surface are recovered and analyzed using a trace amount of analysis liquid. . Specifically, a minute amount of analysis liquid is discharged onto the surface of a substrate such as a silicon wafer, the substrate surface is swept with the discharged analysis liquid to recover impurities, and the recovered analysis liquid is analyzed by an inductively coupled plasma mass spectrometer (ICP-MS). MS), ion chromatography, or the like. For such analysis, a substrate analysis nozzle is used that ejects an analysis liquid from its tip onto a substrate, sweeps the surface of the substrate with the ejected analysis liquid, and then sucks the analysis liquid.
この基板分析用ノズルは、先端から基板上に分析液を吐出し、吐出した分析液で基板表面を掃引した後に分析液を吸引するようになっており、分析液を吐出及び吸引するノズル本体と、掃引する分析液を取り囲むようノズル本体の外周に配置された外管とからなる二重管で構成されたものが知られている（例えば、特許文献１）。この特許文献１に開示された二重管構造の基板分析用ノズルは、短時間で基板表面を掃引可能であり、掃引中に分析液が脱落しにくいという特性がある。
The substrate analysis nozzle discharges the analysis liquid from the tip onto the substrate, sweeps the substrate surface with the discharged analysis liquid, and then sucks the analysis liquid. , and an outer tube arranged on the outer periphery of the nozzle body so as to surround the sweeping analysis liquid (for example, Patent Document 1). The double-tube structure substrate analysis nozzle disclosed in Patent Document 1 is capable of sweeping the substrate surface in a short period of time, and has the characteristic that the analysis liquid is less likely to fall off during the sweep.
この二重管の基板分析用ノズルは、具体的には図１に示すような構造となっている。基板分析用ノズル１は、ノズル本体１０と、外管２０とからなる二重管で構成され、ノズル本体１０は、シリンジポンプ３０とチューブにより接続されており、分析液Ｄがノズル本体１０の先端から吐出可能となっている。また、外管２０には、ノズル本体１０と外管２０との空間を減圧雰囲気になるようにポンプ（図示せず）に接続された吸引手段２１が設けられている。この図１で示す基板分析用ノズルでは、ノズル本体１０の先端部分に保持された分析液Ｄで、分析対象である基板表面を掃引するように移動させる。掃引中は、ノズル本体１０と外管２０との間を減圧雰囲気にすることで、ノズル本体１０の先端部分に保持された分析液が脱落することが防止される。
This double-tube substrate analysis nozzle has a specific structure as shown in FIG. The substrate analysis nozzle 1 is composed of a double tube consisting of a nozzle body 10 and an outer tube 20. The nozzle body 10 is connected to a syringe pump 30 by a tube. It is possible to discharge from. Further, the outer tube 20 is provided with a suction means 21 connected to a pump (not shown) so that the space between the nozzle body 10 and the outer tube 20 becomes a reduced pressure atmosphere. In the substrate analysis nozzle shown in FIG. 1, the analysis liquid D held at the tip of the nozzle body 10 sweeps the surface of the substrate to be analyzed. During the sweep, the atmosphere between the nozzle body 10 and the outer tube 20 is reduced to prevent the analysis liquid held at the tip of the nozzle body 10 from falling off.
ところで、上記先行技術文献記載の基板分析用ノズルであっても、基板表面の親水性が高い場合、分析液を脱落させることなく掃引できても、分析液をノズルに回収するときに、分析液の一部が基板表面上に残存する傾向が生じた。特に、基板表面に存在する陰イオン（塩素イオン、フッ素イオン、硝酸イオン、硫酸イオンなど）を分析する場合では、従来の金属分析における気相分解法が使用できないため、基板表面が酸化膜等の親水性となっており、回収時にかなり多くの分析液が基板表面上に残存することが生じた。分析液の回収率が小さくなると、分析に使用できる量が少なくなるため、より回収率を高くする技術が求められている。
By the way, even with the substrate analysis nozzle described in the prior art document, when the substrate surface is highly hydrophilic, even if the analysis liquid can be swept without falling off, when the analysis liquid is recovered into the nozzle, the analysis liquid tended to remain on the substrate surface. In particular, when analyzing anions (chlorine ions, fluoride ions, nitrate ions, sulfate ions, etc.) existing on the substrate surface, the gas phase decomposition method used in conventional metal analysis cannot be used, so the substrate surface may be covered with oxide films, etc. It became hydrophilic, and a considerable amount of the analysis liquid remained on the substrate surface during recovery. As the recovery rate of the analytical solution decreases, the amount that can be used for analysis decreases, so a technique for increasing the recovery rate is desired.
そこで、本発明は、高い親水性の表面を有する基板であっても、二重管構造の基板分析用ノズルを用いて分析する際に、高い回収率で分析液を回収できる分析液の回収方法を提供することを目的とする。
Therefore, the present invention provides a method for recovering an analysis liquid that can recover an analysis liquid at a high recovery rate when analyzing a substrate having a highly hydrophilic surface using a substrate analysis nozzle with a double-tube structure. intended to provide
上記課題を解決するために、本発明は、分析液を吐出及び吸引できるノズル本体と、ノズル本体の先端に保持されて基板を掃引する分析液を取り囲むようノズル本体の外周に配置された外管とからなり、ノズル本体と外管との間を減圧雰囲気とする吸引手段を備えた基板分析用ノズルを用い、基板表面を掃引した分析液をノズル本体により回収する分析液の回収方法において、分析液により基板表面を掃引する際、ノズル本体と外管との先端の高さ位置は同一に配置されており、掃引終了後、外管の先端を基板表面から離した状態にして、ノズル本体により分析液を回収することを特徴とする。
In order to solve the above-mentioned problems, the present invention provides a nozzle body capable of discharging and sucking an analysis liquid, and an outer tube arranged around the nozzle body so as to surround the analysis liquid held at the tip of the nozzle body and sweeping the substrate. A method for recovering an analytical liquid comprising: using a substrate analyzing nozzle equipped with a suction means for creating a reduced pressure atmosphere between a nozzle body and an outer tube; When sweeping the substrate surface with the liquid, the height position of the tip of the nozzle body and the outer tube is the same. It is characterized by recovering the analytical solution.
本発明のような二重管構造の基板分析用ノズルを用いる場合、従来は次のような手順により分析液の掃引、回収を行っていた。まず、分析開始時は、基板分析用ノズルの先端（ノズル本体の先端と外管の先端との高さ位置は同一）を基板表面近傍にまで移動させる。その状態で分析液をノズル本体の先端から吐出させる。その際、ノズル本体と外管との間は減圧雰囲気にされているため、分析液は外管から漏れ出さない状態で、基板分析用ノズルの先端側に保持される。この分析液が保持された状態で、基板分析用ノズルと基板とを相対移動させることで、分析液により基板表面を掃引する。掃引後、そのままの状態で、ノズル本体の先端から分析液を吸引して回収する。この回収時には、基板表面近傍に基板分析用ノズルの先端が配置された状態、つまり、ノズル本体の先端と外管の先端との高さ位置は同一となっている。このような状態であると、外管の先端は基板表面近傍に配置されているため、外管と基板との表面張力により、外管の先端と基板表面との間隙に分析液を押し留める傾向が強くなり、ノズル本体の先端での分析液の回収時に液割れが生じて、外管に付着した分析液の回収ができない。これに対して、本発明の分析液の回収方法であれば、掃引終了後、外管の先端を基板表面から離した状態にするため、外管の先端と基板表面との間隙が無くなるため、分析液はノズル本体により効率よく回収されることになる。したがって、本発明によれば、高い回収率で分析液を回収することができ、回収後に基板表面に残存する分析液を少なくすることが可能となる。
When using a substrate analysis nozzle with a double-tube structure like the present invention, conventionally, the analysis solution was swept and collected according to the following procedure. First, at the start of analysis, the tip of the substrate analysis nozzle (the tip of the nozzle body and the tip of the outer tube are at the same height position) is moved to the vicinity of the substrate surface. In this state, the analysis liquid is discharged from the tip of the nozzle body. At this time, since the space between the nozzle main body and the outer tube is in a reduced pressure atmosphere, the analysis liquid is held at the tip side of the substrate analysis nozzle without leaking from the outer tube. By relatively moving the substrate analysis nozzle and the substrate while holding the analysis liquid, the substrate surface is swept with the analysis liquid. After sweeping, in this state, the analysis liquid is collected by sucking it from the tip of the nozzle body. At the time of recovery, the tip of the substrate analysis nozzle is arranged near the surface of the substrate, that is, the tip of the nozzle body and the tip of the outer tube are at the same height position. In such a state, since the tip of the outer tube is located near the surface of the substrate, the surface tension between the outer tube and the substrate tends to hold the analysis solution in the gap between the tip of the outer tube and the substrate surface. becomes stronger, cracking occurs when the analysis liquid is recovered at the tip of the nozzle body, and the analysis liquid adhering to the outer tube cannot be recovered. On the other hand, according to the analysis liquid recovery method of the present invention, the tip of the outer tube is separated from the substrate surface after the sweep is completed. The analysis liquid is efficiently collected by the nozzle main body. Therefore, according to the present invention, the analysis liquid can be recovered at a high recovery rate, and the amount of the analysis liquid remaining on the substrate surface after recovery can be reduced.
本発明において、外管の先端を基板表面から離した状態するための基板分析用ノズルの構造には、特に制限はない。例えば、ノズル本体と外管とを着脱可能な構造にしたり、ノズル本体に対して外管が上下に移動可能な構造などを採用することができる。
In the present invention, the structure of the substrate analysis nozzle for keeping the tip of the outer tube away from the substrate surface is not particularly limited. For example, a structure in which the nozzle body and the outer tube are detachable or a structure in which the outer tube can move up and down with respect to the nozzle body can be adopted.
本発明は、親水性の高い基板表面に好適であるが、疎水性の基板表面にも適用できる。また、分析液も、特に制限はなく、フッ化水素と過酸化水素との混合液、王水、超純水などを使用することができる。本発明は、親水性の高い基板表面に対して超純水を用いて分析を行う場合に、特に有効である。
Although the present invention is suitable for highly hydrophilic substrate surfaces, it can also be applied to hydrophobic substrate surfaces. Also, the analysis liquid is not particularly limited, and a mixed liquid of hydrogen fluoride and hydrogen peroxide, aqua regia, ultrapure water, or the like can be used. The present invention is particularly effective when analyzing a highly hydrophilic substrate surface using ultrapure water.
以上説明したように、本発明の分析液の回収方法は、親水性の大きな基板表面であっても、高い回収率で分析液を回収することができ、回収後に基板表面に残存する分析液を少なくすることが可能となる。
INDUSTRIAL APPLICABILITY As described above, the analytical liquid recovery method of the present invention is capable of recovering the analytical liquid at a high recovery rate even on a highly hydrophilic substrate surface, and the analytical liquid remaining on the substrate surface after recovery can be eliminated. can be reduced.
以下、本発明の実施形態について説明する。図２に、本実施形態の基板分析用ノズルの断面図を示す。図２の基板分析用ノズル１は、ノズル本体１０と、外管２０とからなる二重管で構成されており、外管２０はノズル本体１０に対して着脱可能な構造とされ、リング状の磁石２２を介してノズル本体１０に取り付けられている。また、ノズル本体１０は、シリンジポンプ３０とチューブにより接続されており、分析液Ｄが先端側に吐出可能となっている。また、外管１０には、ノズル本体１０と外管２０との空間を減圧雰囲気になるようにポンプ（図示せず）に接続された吸引手段２１が設けられている。尚、ノズル掃引操作は、例えば、基板（ウェーハＷ）を回転させつつノズルを内側から外側に移動させる等の方法で基板Ｗの表面全体に対して任意に行うことができる。
Embodiments of the present invention will be described below. FIG. 2 shows a cross-sectional view of the substrate analysis nozzle of this embodiment. The substrate analysis nozzle 1 shown in FIG. 2 is composed of a double tube consisting of a nozzle body 10 and an outer tube 20. The outer tube 20 is detachable from the nozzle body 10, and has a ring shape. It is attached to the nozzle body 10 via a magnet 22 . Further, the nozzle body 10 is connected to the syringe pump 30 by a tube, so that the analysis liquid D can be discharged to the tip side. Further, the outer tube 10 is provided with a suction means 21 connected to a pump (not shown) so that the space between the nozzle body 10 and the outer tube 20 becomes a reduced pressure atmosphere. The nozzle sweeping operation can be arbitrarily performed on the entire surface of the substrate W by, for example, moving the nozzle from the inside to the outside while rotating the substrate (wafer W).
図２で示す基板分析用ノズルにおいて、ノズル本体１０および外管２０はステンレススチール製またはフッ素樹脂製のものを採用する。ノズル本体１０の先端部口径は０．８～２ｍｍのものを用いることができ、外管の口径は５ｍｍ～４０ｍｍのものを採用することができる。ノズル本体１０の口径は小さい方が、分析液の回収率を高くできる傾向がある。外管の口径は分析液の種類などを考慮して適宜決定する。
In the substrate analysis nozzle shown in FIG. 2, the nozzle body 10 and the outer tube 20 are made of stainless steel or fluororesin. A nozzle body 10 with a tip diameter of 0.8 to 2 mm can be used, and an outer tube with a diameter of 5 mm to 40 mm can be used. The smaller the diameter of the nozzle body 10, the higher the analysis liquid recovery rate tends to be. The diameter of the outer tube is appropriately determined in consideration of the type of analysis liquid.
分析対象の基板として、８インチのＳｉＣウェーハを用い、この基板表面の陰イオンの分析を行うため、分析液として超純水を用いて、分析液の回収率を調べた。ノズル本体の口径は１ｍｍ、外管の口径は２０ｍｍで行った。
An 8-inch SiC wafer was used as the substrate to be analyzed, and ultrapure water was used as the analysis liquid in order to analyze the anions on the surface of this substrate, and the recovery rate of the analysis liquid was investigated. The diameter of the nozzle body was 1 mm, and the diameter of the outer tube was 20 mm.
分析液の回収率は、次のような手順で行った。まず、ノズル本体単独で超純水を既定量（１０００μL）吸引し、その後、ノズル本体と外管との先端が同一の高さ位置になるようにノズル本体に外管を装着し、分析対象の基板の上方から基板分析用ノズルを降下させて、基板分析用ノズルの先端が基板表面から０．５ｍｍ離れた上方に位置するようにした。この操作により、ノズル本体の先端と外管の先端とは、基板表面から０．５ｍｍ離れた上方に位置する、同一の高さに配置された状態となる。その後、１０００μＬの超純水をノズル本体より基板表面へ吐出させて基板表面を掃引した。このとき、吸引手段により、ノズル本体と外管との空間は減圧雰囲気とした。所定の掃引操作を行った後、すべての超純水を基板表面に吐出し、基板分析用ノズルを一旦上昇させる。上昇させた状態で、着脱可能にされた外管をノズル本体から取り外す。その状態で、ノズル本体の先端を基板表面から０．２ｍｍ離れた上方に配置した状態にして、シリンジポンプを用いて超純水を回収した(図３)。超純水の回収量は９５０μＬであった。このことから、本実施形態における回収方法によると、分析液の回収率は９５％であることが判明した。
The recovery rate of the analytical solution was determined according to the following procedure. First, a predetermined amount (1000 μL) of ultrapure water is aspirated by the nozzle body alone, and then the outer tube is attached to the nozzle body so that the tips of the nozzle body and the outer tube are at the same height position, and the analysis target is The substrate analysis nozzle was lowered from above the substrate so that the tip of the substrate analysis nozzle was positioned 0.5 mm above the substrate surface. By this operation, the tip of the nozzle main body and the tip of the outer tube are positioned at the same height above the substrate surface by 0.5 mm. Thereafter, 1000 μL of ultrapure water was discharged from the nozzle body onto the substrate surface to sweep the substrate surface. At this time, the space between the nozzle main body and the outer tube was made to have a reduced pressure atmosphere by the suction means. After performing a predetermined sweeping operation, all the ultrapure water is discharged onto the substrate surface, and the substrate analysis nozzle is once raised. Remove the detachable outer tube from the nozzle main body in the raised state. In this state, the tip of the nozzle body was placed 0.2 mm above the substrate surface, and ultrapure water was recovered using a syringe pump (FIG. 3). The recovered amount of ultrapure water was 950 μL. From this, it was found that the analysis liquid recovery rate was 95% according to the recovery method of the present embodiment.
比較として、従来の回収方法による回収率を調べた。この従来の回収方法は、上述した本実施形態の回収方法における外管着脱を行わず、掃引操作後、そのままの状態で超純水の回収を行うものである。その結果、従来の回収方法によると、吐出量１０００μＬに対して回収量が５００μＬであった。従来の回収方法では、分析液の回収率は５０％であった。
As a comparison, we examined the recovery rate by the conventional recovery method. This conventional recovery method does not involve the attachment and detachment of the outer tube in the recovery method of the present embodiment described above, and recovers ultrapure water in the same state after the sweep operation. As a result, according to the conventional recovery method, the recovery amount was 500 μL with respect to the discharge amount of 1000 μL. In the conventional recovery method, the recovery rate of the analytical liquid was 50%.
本発明は、親水性の大きな基板であっても、高い回収率で分析液を回収することができる。特に、陰イオンの分析において、分析液として超純水を用いる場合、高い回収率で超純水を回収することができるので、
陰イオン分析の分析精度を高めることが可能となる。 INDUSTRIAL APPLICABILITY According to the present invention, an analysis liquid can be recovered at a high recovery rate even with a highly hydrophilic substrate. Especially in the analysis of anions, when ultrapure water is used as the analysis liquid, ultrapure water can be recovered at a high recovery rate.
It is possible to improve the analysis accuracy of anion analysis.
陰イオン分析の分析精度を高めることが可能となる。 INDUSTRIAL APPLICABILITY According to the present invention, an analysis liquid can be recovered at a high recovery rate even with a highly hydrophilic substrate. Especially in the analysis of anions, when ultrapure water is used as the analysis liquid, ultrapure water can be recovered at a high recovery rate.
It is possible to improve the analysis accuracy of anion analysis.
１０ ノズル本体
２０ 外管
２１ 吸引手段
２２ 磁石
３０ シリンジポンプ
Ｗ ウェーハ（基板）
Ｄ 分析液 10nozzle body 20 outer tube 21 suction means 22 magnet 30 syringe pump W wafer (substrate)
D analysis solution
２０ 外管
２１ 吸引手段
２２ 磁石
３０ シリンジポンプ
Ｗ ウェーハ（基板）
Ｄ 分析液 10
D analysis solution
Claims (2)
- 分析液を吐出及び吸引できるノズル本体と、ノズル本体の先端に保持されて基板を掃引する分析液を取り囲むようノズル本体の外周に配置された外管とからなり、ノズル本体と外管との間を減圧雰囲気とする吸引手段を備えた基板分析用ノズルを用い、基板表面を掃引した分析液をノズル本体により回収する分析液の回収方法において、
分析液により基板表面を掃引する際、ノズル本体と外管との先端の高さ位置は同一に配置されており、
掃引終了後、外管の先端を基板表面から離した状態にして、ノズル本体により分析液を回収することを特徴とする分析液の回収方法。 It consists of a nozzle body that can discharge and aspirate an analysis liquid, and an outer tube that is arranged around the outer periphery of the nozzle body so as to surround the analysis liquid that is held at the tip of the nozzle body and sweeps the substrate. In a method for recovering an analysis liquid, the analysis liquid that has been swept over the substrate surface is collected by the nozzle body using a substrate analysis nozzle equipped with a suction means that creates a reduced-pressure atmosphere,
When sweeping the substrate surface with the analysis liquid, the height positions of the tips of the nozzle body and the outer tube are arranged at the same level,
A method for recovering an analytical liquid, comprising recovering the analytical liquid by a nozzle main body with the tip of the outer tube separated from the surface of the substrate after the end of the sweep. - 基板は、親水性の表面を備えたものである請求項１に記載の分析液の回収方法。
2. The method for recovering an analysis liquid according to claim 1, wherein the substrate has a hydrophilic surface.
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| JPH05256749A (en) * | 1992-03-12 | 1993-10-05 | Piyuaretsukusu:Kk | Analysis pretreating instrument and pretreating method using instrument thereof |
| JP2004170222A (en) * | 2002-11-20 | 2004-06-17 | Technos:Kk | Scanning-cum-recovery nozzle |
| JP2006190858A (en) * | 2005-01-07 | 2006-07-20 | Nas Giken:Kk | Substrate treatment apparatus and substrate treatment method |
| JP2013257272A (en) * | 2012-06-14 | 2013-12-26 | Ias Inc | Nozzle for substrate analysis |
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2021
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05256749A (en) * | 1992-03-12 | 1993-10-05 | Piyuaretsukusu:Kk | Analysis pretreating instrument and pretreating method using instrument thereof |
| JP2004170222A (en) * | 2002-11-20 | 2004-06-17 | Technos:Kk | Scanning-cum-recovery nozzle |
| JP2006190858A (en) * | 2005-01-07 | 2006-07-20 | Nas Giken:Kk | Substrate treatment apparatus and substrate treatment method |
| JP2013257272A (en) * | 2012-06-14 | 2013-12-26 | Ias Inc | Nozzle for substrate analysis |
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