JP2021196190A - Analysis container, method for analyzing semiconductor sample, and method for manufacturing semiconductor substrate - Google Patents
Analysis container, method for analyzing semiconductor sample, and method for manufacturing semiconductor substrate Download PDFInfo
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- 238000004458 analytical method Methods 0.000 title claims abstract description 89
- 239000004065 semiconductor Substances 0.000 title claims description 75
- 239000000758 substrate Substances 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 46
- 238000000034 method Methods 0.000 title claims description 30
- 239000012535 impurity Substances 0.000 claims abstract description 49
- 238000011109 contamination Methods 0.000 claims abstract description 36
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 26
- 238000010828 elution Methods 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims description 42
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 238000000354 decomposition reaction Methods 0.000 claims description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 19
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 19
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 19
- 238000011282 treatment Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000009616 inductively coupled plasma Methods 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 description 12
- 238000010304 firing Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
- 229910003460 diamond Inorganic materials 0.000 description 8
- 239000010432 diamond Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 235000012431 wafers Nutrition 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
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- 238000003754 machining Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 239000012808 vapor phase Substances 0.000 description 1
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Sampling And Sample Adjustment (AREA)
- Testing Or Measuring Of Semiconductors Or The Like (AREA)
Abstract
Description
本発明は、分析容器、半導体試料の分析方法および半導体基板の製造方法に関する。 The present invention relates to an analysis container, a method for analyzing a semiconductor sample, and a method for manufacturing a semiconductor substrate.
特許文献１には、シリコン基板を分解昇華させた後に得られた分解残渣を分析することにより、シリコン基板中の不純物分析を行う方法が開示されている。 Patent Document 1 discloses a method of analyzing impurities in a silicon substrate by analyzing the decomposition residue obtained after the silicon substrate is decomposed and sublimated.
半導体デバイスにおいて、シリコン基板等の半導体基板の不純物汚染はデバイス性能を低下させる原因となる。したがって、不純物汚染の少ない半導体基板が求められている。不純物汚染の少ない半導体基板を提供するためには、半導体基板の不純物汚染を分析し、分析結果に基づき必要に応じて半導体基板の製造工程に不純物汚染を低減するための処理を施すことが望ましい。 In semiconductor devices, impurity contamination of semiconductor substrates such as silicon substrates causes device performance to deteriorate. Therefore, there is a demand for a semiconductor substrate with less impurity contamination. In order to provide a semiconductor substrate with less impurity contamination, it is desirable to analyze the impurity contamination of the semiconductor substrate and, if necessary, perform a treatment for reducing the impurity contamination in the semiconductor substrate manufacturing process based on the analysis result.
近年、半導体デバイスの微細化や高集積化に伴い、半導体基板の不純物汚染レベル低減の要求はより一層厳しくなっている。そのため、より微量の不純物汚染を検出するために、従来実現されていた分析感度より更に高い感度で半導体基板の不純物汚染を分析することが求められている。また、半導体基板以外の各種試料についても、より高い感度で不純物汚染の分析が可能となることは望ましい。 In recent years, with the miniaturization and high integration of semiconductor devices, the demand for reducing the level of impurity contamination of semiconductor substrates has become even more stringent. Therefore, in order to detect a trace amount of impurity contamination, it is required to analyze the impurity contamination of the semiconductor substrate with a higher sensitivity than the analysis sensitivity conventionally realized. It is also desirable that various samples other than semiconductor substrates can be analyzed for impurity contamination with higher sensitivity.
以上に鑑み本発明の一態様は、分析対象試料の不純物汚染を高感度で分析することを可能にするための手段を提供することを目的とする。 In view of the above, one aspect of the present invention is to provide a means for enabling highly sensitive analysis of impurity contamination of a sample to be analyzed.
本発明の一態様は、
算術平均粗さＲａが１．００μｍ以下の表面を有し、かつ
Ｃｒ、ＦｅおよびＷの溶出量がそれぞれ０．５ｐｇ／ｃｍ２以下であるフッ素樹脂製の分析容器（以下、単に「分析容器」とも記載する。）、
に関する。
One aspect of the present invention is
An analytical container made of fluororesin having a surface with an arithmetic average roughness Ra of 1.00 μm or less and an elution amount of Cr, Fe and W of 0.5 pg / cm 2 or less, respectively (hereinafter, simply “analytical container””. Also described.),
Regarding.
近年、シリコン基板等の半導体試料の分析のために、耐熱性、耐薬品性等の観点からフッ素樹脂製の分析容器が広く用いられている（例えば特許第３８３２２０４号明細書（特許文献１）の段落００１６参照）。本発明者は、上記目的を達成するために検討を重ねる中で、フッ素樹脂製の分析容器では、この容器に起因するＣｒ、ＦｅおよびＷの混入が多く、これにより半導体試料の分析において分析値のバックグラウンドが高くなってしまうことが分析感度低下の原因となるとの新たな知見を得た。この知見に基づき本発明者は更に鋭意検討を重ねた結果、フッ素樹脂製の分析容器として上記分析容器を使用すれば、分析値のバックグラウンドを下げることができるため、半導体試料の不純物汚染をより高い感度で分析することが可能になることを新たに見出した。 In recent years, for the analysis of semiconductor samples such as silicon substrates, fluororesin-made analysis containers have been widely used from the viewpoint of heat resistance, chemical resistance, etc. (for example, Japanese Patent No. 3832204 (Patent Document 1). See paragraph 0016). The present inventor has been studying to achieve the above object, and in the fluororesin-made analysis container, Cr, Fe and W are often mixed due to this container, which causes the analysis value in the analysis of the semiconductor sample. We have obtained new findings that increasing the background of fluororesin causes a decrease in analytical sensitivity. As a result of further diligent studies based on this finding, the present inventor can lower the background of the analytical values by using the above-mentioned analytical vessel as the fluororesin-made analytical vessel, and thus further contaminate the semiconductor sample with impurities. We have newly found that it is possible to analyze with high sensitivity.
一形態では、上記フッ素樹脂は、ポリテトラフルオロエチレンであることができる。 In one form, the fluororesin can be polytetrafluoroethylene.
一形態では、上記分析容器は、半導体試料分析用の分析容器であることができる。 In one embodiment, the analytical vessel can be an analytical vessel for semiconductor sample analysis.
本発明の一態様は、半導体試料を分解した後に得られた分解残渣を上記分析容器内で加熱することを含む、半導体試料の分析方法（以下、単に「分析方法」とも記載する。）に関する。 One aspect of the present invention relates to a method for analyzing a semiconductor sample (hereinafter, also simply referred to as “analytical method”), which comprises heating the decomposition residue obtained after decomposing the semiconductor sample in the analysis container.
一形態では、上記分析方法は、上記加熱後、前記分析容器内の残留物を回収すること、および回収された残留物中の金属成分を分析すること、を更に含むことができる。 In one embodiment, the analytical method can further include recovering the residue in the analytical vessel after heating and analyzing the metal components in the recovered residue.
一形態では、上記金属成分は、Ｃｒ、ＦｅおよびＷを含むことができる。 In one form, the metal component can include Cr, Fe and W.
一形態では、上記金属成分の分析を、誘導結合プラズマ分析によって行うことができる。 In one embodiment, the analysis of the metal components can be performed by inductively coupled plasma analysis.
一形態では、上記半導体試料は、シリコン基板またはその一部であることができる。 In one form, the semiconductor sample can be a silicon substrate or a part thereof.
本発明の一態様は、
評価対象の製造工程において半導体基板を製造すること、
製造された半導体基板またはその一部の金属不純物汚染レベルを上記分析方法によって分析すること、
上記分析の結果、金属不純物汚染レベルが許容レベルと判定された半導体基板が製造された製造工程において、または金属不純物汚染レベルが許容レベルを超えると判定された製造工程に金属不純物汚染低減処理を施した後にその製造工程において、半導体基板を製造すること、
を含む、半導体基板の製造方法（以下、単に「製造方法」とも記載する。）、
に関する。
One aspect of the present invention is
Manufacturing semiconductor substrates in the manufacturing process to be evaluated,
Analyzing the level of metal impurity contamination of the manufactured semiconductor substrate or a part thereof by the above analysis method,
As a result of the above analysis, metal impurity contamination reduction treatment is applied to the manufacturing process in which the semiconductor substrate whose metal impurity contamination level is determined to be the allowable level is manufactured, or in the manufacturing process in which the metal impurity contamination level is determined to exceed the allowable level. After that, in the manufacturing process, manufacturing a semiconductor substrate,
(Hereinafter, also referred to simply as "manufacturing method"), a method for manufacturing a semiconductor substrate including.
Regarding.
一形態では、上記半導体基板は、シリコン基板であることができる。 In one embodiment, the semiconductor substrate can be a silicon substrate.
一形態では、上記金属不純物は、Ｃｒ、ＦｅおよびＷを含むことができる。 In one form, the metal impurities can include Cr, Fe and W.
本発明の一態様によれば、半導体試料の不純物汚染をより高感度で分析することが可能になる。 According to one aspect of the present invention, impurity contamination of a semiconductor sample can be analyzed with higher sensitivity.
［分析容器］
本発明の一態様は、算術平均粗さＲａが１．００μｍ以下の表面を有し、かつＣｒ、ＦｅおよびＷの溶出量がそれぞれ０．５ｐｇ／ｃｍ２以下であるフッ素樹脂製の分析容器に関する。
以下、上記分析容器について、更に詳細に説明する。
[Analytical vessel]
One aspect of the present invention relates to a fluororesin-made analysis vessel having a surface having an arithmetic average roughness Ra of 1.00 μm or less and having Cr, Fe, and W elution amounts of 0.5 pg / cm 2 or less, respectively. ..
Hereinafter, the analysis container will be described in more detail.
上記分析容器は、フッ素樹脂製である。フッ素樹脂は、フッ素（Ｆ）含有重合性化合物の１種以上の重合体または共重合体である。フッ素樹脂は耐熱性および薬品性に優れるため、フッ素樹脂製の容器は各種分析のための分析容器として好適である。フッ素樹脂の具体例としては、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）等を挙げることができ、より高い耐熱性および耐薬品性を有する点からＰＴＦＥが好ましい。 The analysis container is made of fluororesin. The fluororesin is one or more polymers or copolymers of a fluorine (F) -containing polymerizable compound. Since fluororesin has excellent heat resistance and chemical properties, a fluororesin container is suitable as an analysis container for various analyzes. Specific examples of the fluororesin include polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), and PTFE is preferable because it has higher heat resistance and chemical resistance.
上記分析容器は、算術平均粗さＲａが１．００μｍ以下の表面を有する。かかる表面は、好ましくは分析容器の少なくとも内側底面であることができ、より好ましくは内側底面および内側側面であることができる。本発明および本明細書における算術平均粗さＲａは、原子間力顕微鏡を使用してＪＩＳ Ｂ ０６０１：２０１３にしたがい求められる値である。算術平均粗さＲａは、表面粗さの指標である。粗い表面では表面の凹凸内に不純物成分が入り込んでしまい洗浄等を行っても除去され難い。これに対し、上記算術平均粗さＲａが１．００μｍ以下であることは、分析容器の表面からの不純物成分の除去を容易にすることに寄与し得る。この点から、上記算術平均粗さＲａは、０．９５μｍ以下であることが好ましく、０．９０μｍ以下であることがより好ましい。また、上記算術平均粗さＲａは、例えば０．１０μｍ以上、０．３０μｍ以上、０．５０μｍ以上または０．７０μｍ以上であることができるが、不純物の除去の容易性の観点からは上記算術平均粗さＲａの値は小さいほど好ましいため、上記で例示した値を下回ることも好ましい。 The analysis vessel has a surface having an arithmetic mean roughness Ra of 1.00 μm or less. Such a surface can preferably be at least the inner bottom surface of the analytical vessel, more preferably the inner bottom surface and the inner side surface. The arithmetic mean roughness Ra in the present invention and the present specification is a value obtained according to JIS B 0601: 2013 using an atomic force microscope. Arithmetic mean roughness Ra is an index of surface roughness. On a rough surface, impurity components get into the unevenness of the surface and are difficult to remove even by cleaning. On the other hand, the arithmetic average roughness Ra of 1.00 μm or less may contribute to facilitating the removal of impurity components from the surface of the analysis vessel. From this point, the arithmetic average roughness Ra is preferably 0.95 μm or less, and more preferably 0.90 μm or less. The arithmetic average roughness Ra can be, for example, 0.10 μm or more, 0.30 μm or more, 0.50 μm or more, or 0.70 μm or more, but from the viewpoint of ease of removing impurities, the arithmetic mean Since the smaller the roughness Ra value is, the more preferable it is, it is also preferable that the roughness Ra value is lower than the value exemplified above.
上記分析容器からのＣｒ、ＦｅおよびＷの溶出量は、それぞれ０．５ｐｇ／ｃｍ２以下である。先に記載したように、本発明者の検討により、フッ素樹脂製の分析容器からはＣｒ、ＦｅおよびＷの混入が多いことが明らかになった。これは、フッ素樹脂製の分析容器の製造工程に起因するものと推察される。これに対し、上記分析容器は、フッ素樹脂製であるものの、Ｃｒ、ＦｅおよびＷの溶出量はそれぞれ０．５ｐｇ／ｃｍ２以下である。かかる分析容器を使用することにより、分析値のバックグラウンドを下げることができ、その結果、分析感度を高めることができる。上記分析容器からのＣｒ、ＦｅおよびＷの溶出量は、それぞれ０．５ｐｇ／ｃｍ２以下であり、０．０ｐｇ／ｃｍ２以上０．５ｐｇ／ｃｍ２以下であることができる。 The elution amount of Cr, Fe and W from the analysis vessel is 0.5 pg / cm 2 or less, respectively. As described above, the study of the present inventor has revealed that a large amount of Cr, Fe and W are mixed in the fluororesin-made analysis container. It is presumed that this is due to the manufacturing process of the fluororesin analysis container. On the other hand, although the analysis vessel is made of fluororesin, the elution amounts of Cr, Fe and W are 0.5 pg / cm 2 or less, respectively. By using such an analysis container, the background of the analysis value can be lowered, and as a result, the analysis sensitivity can be increased. The elution amount of Cr, Fe and W from the analysis vessel can be 0.5 pg / cm 2 or less and 0.0 pg / cm 2 or more and 0.5 pg / cm 2 or less, respectively.
本発明および本明細書において、上記溶出量は、以下の方法によって求められる値である。
濃度５０質量％の弗酸、濃度６９．５質量％の硝酸および濃度２０質量％の塩酸の混合液（質量基準の混合比は１：１：１）５ｍｌを測定対象の分析容器の内側底面上に滴下する。この分析容器を設定温度２００℃のホットプレート上に配置して加熱し、分析容器内の液滴が１滴になるまで上記混合液を加熱濃縮する。分析容器をホットプレート上から外して分析容器内の液滴を室温環境（雰囲気温度：２０〜２５℃の範囲）で１時間放冷した後、分析容器内に濃度４質量％の弗酸と濃度４質量％の過酸化水素水溶液との混合液（質量基準の混合比は１：１）１ｍｌを回収液として加え、上記液滴を回収液に取り込んで回収する。上記液滴を取り込んだ回収液を誘導結合プラズマ質量分析装置（ＩＣＰ−ＭＳ）によって分析してＣｒ、ＦｅおよびＷを定量する。こうして得られた定量結果を分析容器の内側底面の面積で除することによって、Ｃｒ、ＦｅおよびＷの溶出量（単位：ｐｇ／ｃｍ２）がそれぞれ求められる。
In the present invention and the present specification, the above-mentioned elution amount is a value obtained by the following method.
On the inner bottom surface of the analysis vessel to be measured, 5 ml of a mixed solution of 50% by mass fluoride, 69.5% by mass nitric acid and 20% by mass hydrochloric acid (mass-based mixing ratio is 1: 1: 1). Drop into. This analysis vessel is placed on a hot plate having a set temperature of 200 ° C. and heated, and the mixed solution is heated and concentrated until the number of droplets in the analysis vessel becomes one. After removing the analysis vessel from the hot plate and allowing the droplets in the analysis vessel to cool in a room temperature environment (atmospheric temperature: range of 20 to 25 ° C.) for 1 hour, the concentration of 4% by mass of fluoroacid is contained in the analysis vessel. 1 ml of a mixed solution with a 4% by mass aqueous hydrogen peroxide solution (mixing ratio based on mass is 1: 1) is added as a recovery solution, and the droplets are taken into the recovery solution for recovery. The recovered liquid containing the droplets is analyzed by an inductively coupled plasma mass spectrometer (ICP-MS) to quantify Cr, Fe and W. By dividing the quantitative result obtained in this way by the area of the inner bottom surface of the analysis vessel, the elution amount of Cr, Fe and W (unit: pg / cm 2 ) can be obtained.
フッ素樹脂製の分析容器は、公知の方法で作製することができる。例えば、フッ素樹脂の粉体を圧縮成形、押出成形、回転成形等の公知の成形方法でブロック状等の成形体に成形した後、この成形体に、研削、切削等の１種以上の機械加工を施すことにより、分析対象試料または分析対象試料の分解残渣を導入可能な凹み部を有する分析容器を得ることができる。分析容器の一例としては、ビーカーを挙げることができる。例えば、成形体の表層部を切削して除去する除去量を多くするほど、成形に使用した金型や成形装置（例えば焼成炉）から成形体の表層部に混入した不純物をより多く除去することができる。また、本発明者の検討によれば、算術平均粗さＲａが１．００μｍを超える表面を有する分析容器については、洗浄を十分行ったとしてもＣｒ、ＦｅおよびＷの溶出量を上記範囲に低減することは容易ではない。これに対し、算術平均粗さＲａが１．００μｍ以下の表面を形成すべく機械加工条件を強化すること、上記のように切削による除去量を多くすること等は、Ｃｒ、ＦｅおよびＷの溶出量を上記範囲に低減することを可能とすることに寄与し得る。 The fluororesin-made analysis container can be produced by a known method. For example, a fluororesin powder is molded into a block-shaped molded product by a known molding method such as compression molding, extrusion molding, or rotary molding, and then the molded product is machined by one or more types such as grinding and cutting. By performing the above, it is possible to obtain an analysis container having a recessed portion into which the sample to be analyzed or the decomposition residue of the sample to be analyzed can be introduced. A beaker can be mentioned as an example of an analysis container. For example, the larger the amount of removal by cutting the surface layer of the molded product, the more impurities mixed in the surface layer of the molded product are removed from the mold and molding equipment (for example, firing furnace) used for molding. Can be done. Further, according to the study of the present inventor, the elution amount of Cr, Fe and W is reduced to the above range even if the analytical vessel having a surface having an arithmetic average roughness Ra exceeding 1.00 μm is sufficiently washed. It's not easy to do. On the other hand, strengthening the machining conditions to form a surface with an arithmetic average roughness Ra of 1.00 μm or less, increasing the amount removed by cutting as described above, etc., elute Cr, Fe and W. It may contribute to making it possible to reduce the amount to the above range.
上記分析容器は、各種試料を分析するための分析容器として用いることができる。分析容器とは、分析対象試料を分析するための１つ以上の工程において使用される容器をいうものとする。上記分析容器は、好ましくは半導体試料分析用の分析容器として用いることができる。 The analysis container can be used as an analysis container for analyzing various samples. The analysis container means a container used in one or more steps for analyzing a sample to be analyzed. The analysis container can be preferably used as an analysis container for semiconductor sample analysis.
［半導体試料の分析方法］
本発明の一態様は、半導体試料を分解した後に得られた分解残渣を上記分析容器内で加熱することを含む半導体試料の分析方法に関する。
[Analysis method for semiconductor samples]
One aspect of the present invention relates to a method for analyzing a semiconductor sample, which comprises heating the decomposition residue obtained after decomposing the semiconductor sample in the analysis vessel.
半導体試料の不純物分析法としては、半導体試料の一部または全部を分解した後、分解残渣中の不純物を定量する方法が挙げられる。かかる分析法において分解残渣を分析容器内で加熱することにより、分析装置の減感等の原因となり得るマトリックス成分（例えばシリコン試料の分解残渣に含まれるＳｉ含有成分）を分解昇華させて除去することができる。しかし、この加熱によってＣｒ、ＦｅおよびＷからなる群から選ばれる成分が浸み出し分解残渣に混入することは、分析感度低下の原因となる。これに対し、上記分析容器によれば、かかる分析感度の低下を抑制することができる。 Examples of the impurity analysis method for a semiconductor sample include a method of decomposing a part or all of the semiconductor sample and then quantifying the impurities in the decomposition residue. In such an analysis method, by heating the decomposition residue in the analysis vessel, the matrix component (for example, the Si-containing component contained in the decomposition residue of the silicon sample) that may cause desensitization of the analyzer is decomposed and sublimated to be removed. Can be done. However, this heating causes a component selected from the group consisting of Cr, Fe, and W to seep out and mix with the decomposition residue, which causes a decrease in analytical sensitivity. On the other hand, according to the analysis container, it is possible to suppress such a decrease in analysis sensitivity.
分析対象の半導体試料としては、シリコン試料等の各種半導体試料を挙げることができる。具体例としては、シリコン基板、シリコン基板から切り出したシリコン試料等が挙げられる。また、シリコンインゴットから切り出したシリコン試料を分析対象とすることもできる。本発明および本明細書において、「シリコン」とは、特記しない限り、単結晶シリコンをいうものとする。 Examples of the semiconductor sample to be analyzed include various semiconductor samples such as a silicon sample. Specific examples include a silicon substrate, a silicon sample cut out from a silicon substrate, and the like. Further, a silicon sample cut out from a silicon ingot can be used as an analysis target. In the present invention and the present specification, "silicon" means single crystal silicon unless otherwise specified.
上記分析方法では、半導体試料の分解も上記分析容器において行ってもよく、半導体試料の分解は上記分析容器とは別の容器または装置において行ってもよい。後者の実施形態では、例えば、回収液を使用して分解残渣を回収して上記分析容器に移すことができる。また、半導体試料の分解は、気相分解または液相分解によって行うことができ、分析感度の観点からは気相分解によって行うことが好ましい。気相分解は、半導体試料をエッチングガスと接触させることによって行うことができる。また、上記分析容器内で分解残渣を加熱する際には、マトリックス成分の分解昇華を促進するために酸溶液を添加した後に加熱することが好ましい。ここで使用可能な酸溶液および分解昇華のための加熱条件、半導体試料の気相分解のために使用可能なエッチングガスおよび気相分解のための処理条件、回収液として使用可能な溶液および回収方法については特に制限はなく、公知技術を適用することができる。一例として、特許第３８３２２０４号明細書（特許文献１）を参照できる。 In the above analysis method, the decomposition of the semiconductor sample may be performed in the above analysis container, and the decomposition of the semiconductor sample may be performed in a container or device different from the above analysis container. In the latter embodiment, for example, a recovery liquid can be used to recover the decomposition residue and transfer it to the analysis vessel. Further, the decomposition of the semiconductor sample can be performed by gas phase decomposition or liquid phase decomposition, and it is preferable to perform the decomposition by gas phase decomposition from the viewpoint of analytical sensitivity. The vapor phase decomposition can be performed by bringing the semiconductor sample into contact with the etching gas. Further, when heating the decomposition residue in the analysis vessel, it is preferable to add an acid solution and then heat the matrix component in order to promote the decomposition and sublimation of the matrix component. Acid solution and heating conditions for decomposition and sublimation that can be used here, etching gas that can be used for gas phase decomposition of semiconductor samples and treatment conditions for gas phase decomposition, solutions that can be used as recovery liquids, and recovery methods. There are no particular restrictions on the above, and known techniques can be applied. As an example, Japanese Patent No. 3832204 (Patent Document 1) can be referred to.
上記分析容器内で分解残渣を加熱することにより、その一部を分解昇華させて除去することができる。この加熱後に残留している残留物を回収し、回収された残留物中の金属成分を分析することにより、分析対象の半導体試料の金属汚染の有無および／または程度を分析することができる。上記残留物の回収方法および金属成分の分析方法については特に制限はなく、公知技術を適用することができる。一例として、特許第３８３２２０４号明細書（特許文献１）を参照できる。金属成分の分析は、例えば、誘導結合プラズマ分析（例えばＩＣＰ−ＭＳ（ＩＣＰ質量分析）、ＩＣＰ−ＡＥＳ（ＩＣＰ発光分光分析））、原子吸光分析（ＡＡＳ）等によって行うことができ、分析精度の観点からは誘導結合プラズマ分析が好ましい。分析対象の金属成分としては、Ｃｒ、ＦｅおよびＷからなる群から選ばれる１種以上を挙げることができ、Ｃｒ、ＦｅおよびＷを分析対象とすることが好ましい。上記分析容器を使用することにより、分析容器に起因する分析感度低下を抑制することができ、Ｃｒ、ＦｅおよびＷを高感度分析することが可能になる。 By heating the decomposition residue in the analysis vessel, a part thereof can be decomposed and sublimated and removed. By recovering the residue remaining after heating and analyzing the metal component in the recovered residue, the presence or absence and / or degree of metal contamination of the semiconductor sample to be analyzed can be analyzed. The method for recovering the residue and the method for analyzing the metal component are not particularly limited, and known techniques can be applied. As an example, Japanese Patent No. 3832204 (Patent Document 1) can be referred to. The analysis of the metal component can be performed by, for example, inductively coupled plasma analysis (for example, ICP-MS (ICP mass analysis), ICP-AES (ICP emission spectroscopic analysis)), atomic absorption spectrometry (AAS), etc. From the viewpoint, inductively coupled plasma analysis is preferable. As the metal component to be analyzed, one or more selected from the group consisting of Cr, Fe and W can be mentioned, and it is preferable to use Cr, Fe and W as the analysis target. By using the above-mentioned analysis container, it is possible to suppress the decrease in analysis sensitivity caused by the analysis container, and it becomes possible to perform high-sensitivity analysis of Cr, Fe and W.
［半導体基板の製造方法］
本発明の一態様は、
評価対象の製造工程において半導体基板を製造すること、
製造された半導体基板またはその一部の金属不純物汚染レベルを上記分析方法によって分析すること、
上記分析の結果、金属不純物汚染レベルが許容レベルと判定された半導体基板が製造された製造工程において、または金属不純物汚染レベルが許容レベルを超えると判定された製造工程に金属不純物汚染低減処理を施した後にその製造工程において、半導体基板を製造すること、
を含む、半導体基板の製造方法、
に関する。
[Manufacturing method of semiconductor substrate]
One aspect of the present invention is
Manufacturing semiconductor substrates in the manufacturing process to be evaluated,
Analyzing the level of metal impurity contamination of the manufactured semiconductor substrate or a part thereof by the above analysis method,
As a result of the above analysis, metal impurity contamination reduction treatment is applied to the manufacturing process in which the semiconductor substrate whose metal impurity contamination level is determined to be the allowable level is manufactured, or in the manufacturing process in which the metal impurity contamination level is determined to exceed the allowable level. After that, in the manufacturing process, manufacturing a semiconductor substrate,
Manufacturing method of semiconductor substrate, including
Regarding.
半導体基板の金属汚染は、製造工程に起因して発生し得る。上記製造方法は、先に記載した本発明の一態様にかかる分析方法によって工程評価用の半導体試料（半導体基板またはその一部）の金属不純物汚染レベルの分析を行い、この分析の結果に基づき、上記工程評価用の半導体試料が製造された製造工程における金属不純物汚染レベルを評価する。この評価の結果、金属不純物汚染レベルが許容レベルを超えると判定された場合には、製造工程に金属不純物汚染低減処理を施すことにより、かかる処理後に当該製造工程において金属不純物汚染が少ない半導体基板を安定的に量産することが可能になる。または、上記判定の結果、金属不純物汚染低減処理が不要（即ち金属不純物汚染レベルが許容レベル）と判定された製造工程では、金属不純物汚染低減処理を行うことなく、金属不純物汚染が少ない半導体基板を引き続き安定的に量産することができる。分析対象の金属不純物としては、Ｃｒ、ＦｅおよびＷからなる群から選ばれる１種以上を挙げることができ、Ｃｒ、ＦｅおよびＷを分析対象とすることが好ましい。 Metallic contamination of semiconductor substrates can occur due to the manufacturing process. In the above manufacturing method, the metal impurity contamination level of the semiconductor sample (semiconductor substrate or a part thereof) for process evaluation is analyzed by the analysis method according to one aspect of the present invention described above, and based on the result of this analysis, The level of metal impurity contamination in the manufacturing process in which the semiconductor sample for process evaluation is manufactured is evaluated. As a result of this evaluation, if it is determined that the metal impurity contamination level exceeds the permissible level, a metal impurity contamination reduction treatment is applied to the manufacturing process to obtain a semiconductor substrate having less metal impurity contamination in the manufacturing process after such treatment. Stable mass production becomes possible. Alternatively, in the manufacturing process in which it is determined that the metal impurity contamination reduction treatment is unnecessary as a result of the above determination (that is, the metal impurity contamination level is an acceptable level), a semiconductor substrate with less metal impurity contamination is used without performing the metal impurity contamination reduction treatment. It can continue to be mass-produced in a stable manner. Examples of the metal impurity to be analyzed include one or more selected from the group consisting of Cr, Fe and W, and it is preferable to use Cr, Fe and W as the analysis target.
上記製造工程は、シリコン基板（シリコンウェーハ）等の半導体基板の製造工程として公知の製造工程であることができ、特に限定されるものではない。例えば、半導体インゴットから切り出された半導体ウェーハに、各種研削および／または研磨処理を施してポリッシュドウェーハを製造する製造工程、更にアニール処理を含むアニールウェーハの製造工程等を例示できる。金属不純物汚染低減処理としては、例えば、製造工程に含まれる部材、配管、装置等の交換、洗浄、補修等、製造工程で使用される薬液の交換、高純度化等、プロセスガスの高純度化等を挙げることができる。 The manufacturing process can be a manufacturing process known as a manufacturing process of a semiconductor substrate such as a silicon substrate (silicon wafer), and is not particularly limited. For example, a manufacturing process for manufacturing a polished wafer by subjecting a semiconductor wafer cut out from a semiconductor ingot to various grinding and / or polishing treatments, a manufacturing process for annealed wafers including an annealing treatment, and the like can be exemplified. Metal impurity contamination reduction treatment includes, for example, replacement, cleaning, repair, etc. of members, pipes, equipment, etc. included in the manufacturing process, replacement of chemicals used in the manufacturing process, high purification, etc., and high purification of process gas. And so on.
上記製造方法のその他の詳細については、半導体基板の製造に関する公知技術を適用できる。 For other details of the above manufacturing method, known techniques for manufacturing semiconductor substrates can be applied.
以下に、本発明を実施例に基づき更に説明する。ただし、本発明は実施例に示す実施態様に限定されるものではない。以下に記載の各種工程および評価は、特記しない限り、大気圧下、室温（２０〜２５℃）の雰囲気中で行われた。また、各種薬液の液温は、特記しない限り、室温（２０〜２５℃）である。 Hereinafter, the present invention will be further described based on examples. However, the present invention is not limited to the embodiments shown in the examples. Unless otherwise specified, the various steps and evaluations described below were performed under atmospheric pressure in an atmosphere at room temperature (20 to 25 ° C.). The temperature of various chemicals is room temperature (20 to 25 ° C.) unless otherwise specified.
［実施例１］
ＰＴＦＥパウダーを直径１００ｍｍ、高さ１００ｍｍの円柱状に圧縮成形し、３５０〜４００℃の焼成温度で焼成し、直径１００ｍｍ、高さ１００ｍｍの円柱状のＰＴＦＥブロックを得た。焼成温度とは、焼成を行う焼成炉の炉内雰囲気温度をいうものとする。ダイヤモンドバイトを用いて、このＰＴＦＥブロックの全表面を切削し、直径６５ｍｍ、高さ７０ｍｍの円柱状のＰＴＦＥブロックにした。具体的には、円柱状のＰＴＦＥブロックの側面を切削代１７．５ｍｍの切削量で切削して直径６５ｍｍのブロックとした後、上面および下面をそれぞれ切削代１５ｍｍの切削量で切削した。このブロックを、ダイヤモンドバイトを用いて切削加工し、外径６５ｍｍ、内径５５ｍｍ、高さ７０ｍｍ、深さ６７ｍｍのビーカーを作製した。このビーカーの全表面をダイヤモンドバイトを用いて仕上げ切削した。
仕上げ切削後、ビーカー全体を界面活性剤によって１回洗浄し、その後有機溶剤によって１回洗浄した。その後、弗酸／硝酸／塩酸をビーカー内部に満たした状態で、設定温度２００℃のホットプレート上にビーカーを１時間配置して加熱洗浄を行った。この加熱洗浄を複数回繰り返した。
[Example 1]
The PTFE powder was compression-molded into a cylinder having a diameter of 100 mm and a height of 100 mm, and fired at a firing temperature of 350 to 400 ° C. to obtain a cylindrical PTFE block having a diameter of 100 mm and a height of 100 mm. The firing temperature refers to the atmospheric temperature inside the firing furnace at which firing is performed. The entire surface of this PTFE block was cut using a diamond bite to obtain a cylindrical PTFE block having a diameter of 65 mm and a height of 70 mm. Specifically, the side surface of the columnar PTFE block was cut with a cutting amount of 17.5 mm to obtain a block having a diameter of 65 mm, and then the upper surface and the lower surface were each cut with a cutting amount of 15 mm. This block was cut using a diamond bite to produce a beaker having an outer diameter of 65 mm, an inner diameter of 55 mm, a height of 70 mm, and a depth of 67 mm. The entire surface of this beaker was finished and cut using a diamond bite.
After the finish cutting, the entire beaker was washed once with a surfactant and then once with an organic solvent. Then, with the inside of the beaker filled with phosphoric acid / nitric acid / hydrochloric acid, the beaker was placed on a hot plate having a set temperature of 200 ° C. for 1 hour to perform heat washing. This heat washing was repeated multiple times.
［比較例１］
ＰＴＦＥパウダーを直径７０ｍｍ、高さ７０ｍｍの円柱状に圧縮成形し、３５０〜４００℃の焼成温度で焼成し、直径７０ｍｍ、高さ７０ｍｍの円柱状のＰＴＦＥブロックを得た。このブロックを、ダイヤモンドバイトを用いて切削加工し、外径６５ｍｍ、内径５５ｍｍ、高さ７０ｍｍ、深さ６７ｍｍのビーカーを作製した。このビーカーの全表面を、ダイヤモンドバイトを用いて仕上げ切削した。
仕上げ切削後、実施例１と同様に界面活性剤洗浄、有機溶剤洗浄および加熱洗浄を行った。
[Comparative Example 1]
The PTFE powder was compression-molded into a cylinder having a diameter of 70 mm and a height of 70 mm and fired at a firing temperature of 350 to 400 ° C. to obtain a cylindrical PTFE block having a diameter of 70 mm and a height of 70 mm. This block was cut using a diamond bite to produce a beaker having an outer diameter of 65 mm, an inner diameter of 55 mm, a height of 70 mm, and a depth of 67 mm. The entire surface of this beaker was finished and cut using a diamond bite.
After the finish cutting, surfactant cleaning, organic solvent cleaning, and heat cleaning were performed in the same manner as in Example 1.
［比較例２］
ＰＴＦＥパウダーを直径１００ｍｍ、高さ１００ｍｍの円柱状に圧縮成形し、３５０〜４００℃の焼成温度で焼成し、直径１００ｍｍ、高さ１００ｍｍのＰＴＦＥブロックを得た。ダイヤモンドバイトを用いて、このＰＴＦＥブロックの全表面を、実施例１と同様に切削し、直径６５ｍｍ、高さ７０ｍｍの円柱状のＰＴＦＥブロックにした。このブロックを、ダイヤモンドバイトを用いて切削加工し、外径６５ｍｍ、内径５５ｍｍ、高さ７０ｍｍ、深さ６７ｍｍのビーカーを作製した。このビーカーには、ダイヤモンドバイトによる仕上げ切削は行わなかった。
作製したビーカーに、実施例１と同様に界面活性剤洗浄、有機溶剤洗浄および加熱洗浄を行った。
[Comparative Example 2]
The PTFE powder was compression-molded into a cylinder having a diameter of 100 mm and a height of 100 mm and fired at a firing temperature of 350 to 400 ° C. to obtain a PTFE block having a diameter of 100 mm and a height of 100 mm. Using a diamond bite, the entire surface of this PTFE block was cut in the same manner as in Example 1 to obtain a cylindrical PTFE block having a diameter of 65 mm and a height of 70 mm. This block was cut using a diamond bite to produce a beaker having an outer diameter of 65 mm, an inner diameter of 55 mm, a height of 70 mm, and a depth of 67 mm. This beaker was not finished cut with a diamond bite.
The prepared beaker was washed with a surfactant, an organic solvent and a heat in the same manner as in Example 1.
上記の各ＰＴＦＥ製ビーカーの内側底面、内側側面および外側側面について算術平均粗さＲａを測定したところ、各面のＲａはいずれも表１に示す値であった。 When the arithmetic mean roughness Ra was measured for the inner bottom surface, the inner side surface, and the outer side surface of each of the above-mentioned PTFE beakers, the Ra of each surface was the value shown in Table 1.
上記の各ＰＴＦＥ製ビーカーについて、先に記載した方法によってＣｒ、Ｆｅ、Ｗの溶出量を求めたところ、表１に示す値であった。 When the amount of Cr, Fe, and W eluted from each of the above PTFE beakers was determined by the method described above, the values shown in Table 1 were obtained.
Ｃｒ、ＦｅおよびＷは、焼成時に使用された金型および／または焼成炉由来の金属不純物と推察される。実施例１では、比較例１と比べてＰＴＦＥブロックの切削量が多く、かつビーカー表面のＲａが１．００μｍ以下であり比較例２と比べて表面粗さが低減されているため洗浄によって金属不純物の除去が容易だったことが、実施例１と比較例１、２との金属溶出量の違いの理由であると本発明者は考えている。 Cr, Fe and W are presumed to be metal impurities derived from the mold and / or the firing furnace used at the time of firing. In Example 1, the amount of cutting of the PTFE block is larger than that of Comparative Example 1, the Ra of the beaker surface is 1.00 μm or less, and the surface roughness is reduced as compared with Comparative Example 2. Therefore, metal impurities are formed by cleaning. The present inventor considers that the ease of removal of the metal is the reason for the difference in the amount of metal elution between Example 1 and Comparative Examples 1 and 2.
縦２５０ｍｍ、横２５０ｍｍ、高さ１５０ｍｍ、厚さ２ｍｍのポリプロピレン製の収容容器と蓋からなる反応容器を用意した。
濃度５０質量％の弗酸２５０ｇと濃度６８質量％の硝酸８０ｇと濃度９８質量％の硫酸２５０ｇを混合して分解液を調製した。この分解液を収容容器に添加した。
実施例１、比較例１、比較例２のビーカーを各１個用意し、これらビーカーを収容容器内にそれぞれ配置した。分析対象試料として、ボロンを１×１０１８ａｔｏｍｓ／ｃｍ３ドープしたシリコンウェーハから切断片（５ｇ）を３つ切り出した。分析対象試料を各ビーカー内に入れた後、収容容器に蓋をして反応容器内を密閉状態に保ち、室温で約１２時間放置して分析対象試料を気相分解させて分解残渣を得た。反応容器から分解残渣の入ったビーカーを取出し、濃度３８質量％の弗酸と濃度６８質量％の硝酸を質量比で弗酸：硝酸＝２：１の割合で混合した混酸を分解残渣５ｇ当たり１．０ｍｌ滴下し、更に濃度２０質量％の塩酸と濃度６８質量％の硝酸と濃度９８質量％の硫酸を質量比で弗酸：硝酸：硫酸＝５０：２５：１の割合で混合した混酸を分解残渣５ｇ当たり１．０ｍｌ滴下し、ビーカーを設定温度１５０〜２２０℃のホットプレート上で加熱して分解残渣を分解昇華させた。引き続きビーカーを設定温度１５０〜２２０℃のホットプレート上で加熱して残留物から硫酸を完全に気化させた後、ビーカーをホットプレート上から外し、ビーカー内の残留物を弗酸と硝酸との混合希薄水溶液で回収し、回収した液をＩＣＰ−ＭＳに導入してＣｒ、 Ｆｅ、Ｗの定量分析を行った。分析結果を表２に示す。
A reaction container consisting of a polypropylene storage container having a length of 250 mm, a width of 250 mm, a height of 150 mm, and a thickness of 2 mm and a lid was prepared.
A decomposition solution was prepared by mixing 250 g of phosphoric acid having a concentration of 50% by mass, 80 g of nitric acid having a concentration of 68% by mass, and 250 g of sulfuric acid having a concentration of 98% by mass. This decomposition liquid was added to the container.
One beaker of Example 1, Comparative Example 1, and Comparative Example 2 were prepared, and these beakers were placed in the storage container, respectively. As a sample to be analyzed, three cut pieces (5 g) were cut out from a silicon wafer doped with 1 × 10 18 atoms / cm3 of boron. After the sample to be analyzed was placed in each beaker, the container was covered with a lid to keep the inside of the reaction vessel in a closed state, and the sample to be analyzed was left at room temperature for about 12 hours for gas phase decomposition to obtain a decomposition residue. .. A beaker containing the decomposition residue was taken out from the reaction vessel, and a mixed acid in which a concentration of 38% by mass of fluoroacid and a concentration of 68% by mass of nitric acid were mixed in a mass ratio of fluoroacid: nitric acid = 2: 1 was mixed with 1 per 5 g of the decomposition residue. .0 ml was added dropwise, and a mixed acid in which 20% by mass of hydrochloric acid, 68% by mass of nitrate and 98% by mass of sulfuric acid were mixed in a mass ratio of fluoride: nitrate: sulfuric acid = 50:25: 1 was decomposed. 1.0 ml was added dropwise per 5 g of the residue, and the beaker was heated on a hot plate having a set temperature of 150 to 220 ° C. to decompose and sublimate the decomposition residue. Continue to heat the beaker on a hot plate with a set temperature of 150-220 ° C to completely vaporize the sulfuric acid from the residue, then remove the beaker from the hot plate and mix the residue in the beaker with fluoride and nitric acid. It was recovered with a dilute aqueous solution, and the recovered liquid was introduced into ICP-MS to perform quantitative analysis of Cr, Fe, and W. The analysis results are shown in Table 2.
表２に示すように、比較例１、２では、定量分析結果がビーカー（分析容器）の影響を受けてしまい、低濃度の金属不純物の分析を行うことはできなかった。
これに対し、実施例１では、分析感度が高く、低濃度の金属不純物の定量分析が可能であった。
As shown in Table 2, in Comparative Examples 1 and 2, the quantitative analysis results were affected by the beaker (analytical container), and it was not possible to analyze low-concentration metal impurities.
On the other hand, in Example 1, the analysis sensitivity was high and quantitative analysis of low-concentration metal impurities was possible.
本発明の一態様は、半導体基板の技術分野において有用である。 One aspect of the present invention is useful in the technical field of semiconductor substrates.
Claims (11)
Ｃｒ、ＦｅおよびＷの溶出量がそれぞれ０．５ｐｇ／ｃｍ２以下であるフッ素樹脂製の分析容器。 An analytical container made of fluororesin having a surface with an arithmetic average roughness Ra of 1.00 μm or less and an elution amount of Cr, Fe and W of 0.5 pg / cm 2 or less, respectively.
回収された残留物中の金属成分を分析すること、
を更に含む、請求項４に記載の半導体試料の分析方法。 After the heating, recovering the residue in the analysis vessel, and analyzing the metal component in the recovered residue,
The method for analyzing a semiconductor sample according to claim 4, further comprising.
製造された半導体基板またはその一部の金属不純物汚染レベルを請求項４〜８のいずれか１項に記載の分析方法によって分析すること、
前記分析の結果、金属不純物汚染レベルが許容レベルと判定された半導体基板が製造された製造工程において、または金属不純物汚染レベルが許容レベルを超えると判定された製造工程に金属不純物汚染低減処理を施した後に該製造工程において、半導体基板を製造すること、
を含む、半導体基板の製造方法。 Manufacturing semiconductor substrates in the manufacturing process to be evaluated,
Analyzing the level of metal impurity contamination of the manufactured semiconductor substrate or a part thereof by the analysis method according to any one of claims 4 to 8.
As a result of the above analysis, the metal impurity contamination reduction treatment is performed in the manufacturing process in which the semiconductor substrate whose metal impurity contamination level is determined to be the allowable level is manufactured, or in the manufacturing process in which the metal impurity contamination level is determined to exceed the allowable level. After that, in the manufacturing process, manufacturing a semiconductor substrate,
A method for manufacturing a semiconductor substrate, including.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10253511A (en) * | 1997-03-07 | 1998-09-25 | Toshiba Ceramics Co Ltd | Container for sample for impurity analysis |
| US5849597A (en) * | 1996-12-18 | 1998-12-15 | Toshiba Ceramics Co., Ltd. | Treatment apparatus for high-precision analysis of impurities in silicic material |
| JP2000035424A (en) * | 1998-07-17 | 2000-02-02 | Mitsubishi Materials Silicon Corp | Impurity analyzing method of silicon substrate and its vapor phase cracking device |
| JP2000266650A (en) * | 1999-03-16 | 2000-09-29 | Toshiba Ceramics Co Ltd | Method for analyzing surface-layer impurity of polysilicon, and sample-treating container for etching polysilicon |
| JP2005326240A (en) * | 2004-05-13 | 2005-11-24 | Toshiba Corp | Analyzing container and method for analyzing very small amount of element |
| JP2016119332A (en) * | 2014-12-18 | 2016-06-30 | 信越半導体株式会社 | Manufacturing method of recovery instrument, recovery method of metal impurity, and analysis method of metal impurity |
-
2020
- 2020-06-10 JP JP2020100707A patent/JP2021196190A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5849597A (en) * | 1996-12-18 | 1998-12-15 | Toshiba Ceramics Co., Ltd. | Treatment apparatus for high-precision analysis of impurities in silicic material |
| JPH10253511A (en) * | 1997-03-07 | 1998-09-25 | Toshiba Ceramics Co Ltd | Container for sample for impurity analysis |
| JP2000035424A (en) * | 1998-07-17 | 2000-02-02 | Mitsubishi Materials Silicon Corp | Impurity analyzing method of silicon substrate and its vapor phase cracking device |
| JP2000266650A (en) * | 1999-03-16 | 2000-09-29 | Toshiba Ceramics Co Ltd | Method for analyzing surface-layer impurity of polysilicon, and sample-treating container for etching polysilicon |
| JP2005326240A (en) * | 2004-05-13 | 2005-11-24 | Toshiba Corp | Analyzing container and method for analyzing very small amount of element |
| JP2016119332A (en) * | 2014-12-18 | 2016-06-30 | 信越半導体株式会社 | Manufacturing method of recovery instrument, recovery method of metal impurity, and analysis method of metal impurity |
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