JPH0964052A - Silicon wafer and manufacture thereof - Google Patents
Silicon wafer and manufacture thereofInfo
- Publication number
- JPH0964052A JPH0964052A JP24357595A JP24357595A JPH0964052A JP H0964052 A JPH0964052 A JP H0964052A JP 24357595 A JP24357595 A JP 24357595A JP 24357595 A JP24357595 A JP 24357595A JP H0964052 A JPH0964052 A JP H0964052A
- Authority
- JP
- Japan
- Prior art keywords
- silicon wafer
- wafer
- bulk
- solution
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明はシリコンウェーハ
およびその製造方法、詳しくはシリコンウェーハのバル
ク中および表面のＣｕ（銅）の濃度をコントロールした
シリコンウェーハおよびこのシリコンウェーハの製造方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicon wafer and a method for manufacturing the same, and more particularly to a silicon wafer in which the concentration of Cu (copper) in the bulk and surface of the silicon wafer is controlled and a method for manufacturing this silicon wafer.
【０００２】[0002]
【従来の技術】シリコンウェーハにあって、汚染の機会
が多く、かつ、濃度が高い不純物としてＣｕがある。Ｃ
ｕは結晶中の濃度が極微量であっても、その結晶の電気
特性や結晶特性を左右する。このシリコンウェーハのＣ
ｕ汚染は、例えば研磨工程（ウェーハ内部への汚染）、
洗浄工程（ウェーハ表面の汚染）、あるいは熱処理炉工
程（ウェーハ全体への汚染）等で生じる。Ｃｕは他の重
金属に比較して拡散速度が速いからである。そして、バ
ルク中に拡散したＣｕは洗浄では除去することができ
ず、表面に付着したＣｕも除去しづらいのが現状であ
る。そこで、このＣｕをウェーハ表面およびバルク中か
ら除去することが重要であり、各種の方策（例えばＢＳ
Ｄによるゲッタリング）が講じられている。2. Description of the Related Art In a silicon wafer, Cu is an impurity that has a high chance of contamination and has a high concentration. C
Even if the concentration of u in the crystal is extremely small, u affects the electrical characteristics and crystal characteristics of the crystal. C of this silicon wafer
The u contamination is, for example, a polishing process (contamination inside the wafer),
It occurs in a cleaning process (contamination of the wafer surface) or a heat treatment furnace process (contamination of the entire wafer). This is because Cu has a higher diffusion rate than other heavy metals. The Cu diffused in the bulk cannot be removed by washing, and it is difficult to remove the Cu adhering to the surface. Therefore, it is important to remove this Cu from the wafer surface and in the bulk, and various measures (for example, BS
Gettering by D) is taken.
【０００３】ところで、このシリコンウェーハ表面のＣ
ｕ濃度の測定・分析としては、従来よりＡＡＳ分析また
はＳＩＭＳによることが知られていた。そして、これら
の方法によれば、ウェーハ表面のＣｕ濃度は１０16／ｃ
ｍ3程度であった。すなわち、これより低濃度のＣｕを
有するシリコンウェーハは知られていなかった。By the way, C on the surface of the silicon wafer
As the measurement and analysis of the u concentration, it has been conventionally known to use AAS analysis or SIMS. According to these methods, the Cu concentration on the wafer surface is 10 16 / c.
It was about m 3 . That is, a silicon wafer having a lower concentration of Cu than this has not been known.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、このよ
うな従来のシリコンウェーハにあっては、Ｃｕの汚染濃
度が高いため、その電気特性・結晶特性に悪影響を与え
ているという課題があった。However, in such a conventional silicon wafer, there is a problem in that the electrical and crystalline characteristics of the conventional silicon wafer are adversely affected due to the high contamination concentration of Cu.
【０００５】そこで、発明者は、Ｃｕ汚染について鋭意
研究の結果、以下の知見を得た。すなわち、シリコン
ウェーハのバルク中のＣｕは６００℃以下（例えば室
温）であってもそのウェーハ表面に拡散し、ゲッタリン
グされる。そして、拡散により表面に析出してきたＣ
ｕはＨＦ溶液等の洗浄液により容易に除去することがで
きる。この２点の知見を得て、発明者は以下の発明をな
したものである。Therefore, as a result of earnest research on Cu contamination, the inventor has obtained the following knowledge. That is, Cu in the bulk of a silicon wafer is diffused and gettered on the wafer surface even at 600 ° C. or lower (for example, room temperature). Then, C which has been deposited on the surface by diffusion
u can be easily removed with a cleaning solution such as an HF solution. Based on these two findings, the inventor has made the following inventions.
【０００６】[0006]
【発明の目的】そこで、この発明は、シリコンウェーハ
表面および／またはバルク中のＣｕ濃度を低減したシリ
コンウェーハを得ることを、その目的としている。ま
た、その電気特性（酸化膜耐圧等）・結晶特性の高めら
れたシリコンウェーハを得ることを、その目的としてい
る。また、Ｃｕ汚染されたシリコンウェーハからＣｕを
ゲッタリング可能なシリコンウェーハの製造方法を提供
することを、その目的としている。SUMMARY OF THE INVENTION Therefore, the object of the present invention is to obtain a silicon wafer having a reduced Cu concentration on the surface of the silicon wafer and / or in the bulk. Further, the purpose is to obtain a silicon wafer having improved electrical characteristics (oxide film breakdown voltage, etc.) and crystal characteristics. Moreover, it aims at providing the manufacturing method of the silicon wafer which can getter Cu from the silicon wafer contaminated by Cu.
【０００７】[0007]
【課題を解決するための手段】請求項１に記載の発明
は、シリコンウェーハを６００℃以下で熱処理した後、
その表面を洗浄したシリコンウェーハである。According to a first aspect of the present invention, after a silicon wafer is heat treated at 600 ° C. or lower,
It is a silicon wafer whose surface is cleaned.
【０００８】請求項２に記載の発明は、上記シリコンウ
ェーハ表面のＣｕ濃度は１×１０9個／ｃｍ2以下である
請求項１に記載のシリコンウェーハである。The invention according to claim 2 is the silicon wafer according to claim 1, wherein the Cu concentration on the surface of the silicon wafer is 1 × 10 9 pieces / cm 2 or less.
【０００９】請求項３に記載した発明は、シリコンウェ
ーハを６００℃以下の温度で熱処理する工程と、この後
シリコンウェーハ表面を洗浄する工程と、を備えたシリ
コンウェーハの製造方法である。ウェーハ表面の洗浄
は、例えばＨＦ溶液・ＨＦ／Ｈ2Ｏ2溶液・ＨＣｌ溶液・
ＨＣｌ／Ｈ2Ｏ2溶液・ＨＣｌ／ＨＦ溶液・ＳＣ１溶液・
Ｈ2ＳＯ4／Ｈ2Ｏ2溶液等を用いることができる。A third aspect of the present invention is a method for manufacturing a silicon wafer, which comprises a step of heat-treating the silicon wafer at a temperature of 600 ° C. or lower, and a step of cleaning the surface of the silicon wafer thereafter. For cleaning the wafer surface, for example, HF solution, HF / H 2 O 2 solution, HCl solution,
HCl / H 2 O 2 solution ・ HCl / HF solution ・ SC1 solution ・
An H 2 SO 4 / H 2 O 2 solution or the like can be used.
【００１０】[0010]
【作用】この発明に係るシリコンウェーハでは、表面お
よびバルク中のＣｕ濃度を低減することができる。ま
た、このようにＣｕ濃度を低減したシリコンウェーハに
あっては、その電気特性・結晶特性を高めることができ
る。また、熱処理およびフッ酸溶液等の洗浄液処理によ
り製造したシリコンウェーハでは、そのウェーハ表面の
Ｃｕだけでなくバルク中のＣｕをも除去することがで
き、上記電気特性・結晶特性をさらに高めることができ
る。In the silicon wafer according to the present invention, the Cu concentration on the surface and in the bulk can be reduced. In addition, in such a silicon wafer having a reduced Cu concentration, its electrical characteristics and crystal characteristics can be improved. Further, in a silicon wafer manufactured by heat treatment and treatment with a cleaning solution such as a hydrofluoric acid solution, not only Cu on the surface of the wafer but also Cu in the bulk can be removed, and the electrical characteristics and crystal characteristics can be further enhanced. .
【００１１】[0011]
【発明の実施の形態】以下、この発明の実施例を図面を
参照して説明する。図１は、この発明の一実施例に係る
シリコンウェーハのＣｕ汚染の分析方法を示す工程図で
ある。図２は、この方法によるシリコンウェーハ表面で
のＣｕの回収率を示している。図３は、この発明の一実
施例に係るＣｕフリーのシリコンウェーハの製造方法を
示すフローチャートである。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a process diagram showing a method for analyzing Cu contamination of a silicon wafer according to an embodiment of the present invention. FIG. 2 shows the recovery rate of Cu on the surface of a silicon wafer by this method. FIG. 3 is a flowchart showing a method of manufacturing a Cu-free silicon wafer according to an embodiment of the present invention.
【００１２】図１に示すように、バルク中にＣｕ汚染の
生じたシリコンウェーハで表面に酸化膜を有する場合、
まず、所定のＨＦ溶液（２０％〜５０％，１０分間の浸
漬）で洗浄してこの表面酸化膜（ＳｉＯ2）を除去す
る。次に、このシリコンウェーハを、その鏡面側を上に
して、清浄なシリコンウェーハ上に載置する。この清浄
なシリコンウェーハはホットプレート（表面はセラミッ
クス製）上に載置されている。As shown in FIG. 1, when a silicon wafer having Cu contamination in the bulk has an oxide film on the surface,
First, the surface oxide film (SiO 2 ) is removed by cleaning with a predetermined HF solution (20% to 50%, immersion for 10 minutes). Next, this silicon wafer is placed on a clean silicon wafer with its mirror surface side facing up. This clean silicon wafer is placed on a hot plate (the surface of which is made of ceramics).
【００１３】このシリコンウェーハがＰタイプの場合、
大気中で５００℃・１５分間の加熱を行う。Ｎタイプの
場合、５００℃で２時間の加熱を行う。この環境はウェ
ーハを汚染しないクリーンルームで行う。なお、ホット
プレートに代えて熱処理炉でシリコンウェーハを加熱し
てもよい。この場合、大気中、Ｎ2／Ｏ2、または、Ａｒ
／Ｏ2雰囲気中で加熱するものとする。When this silicon wafer is of P type,
Heat at 500 ° C for 15 minutes in the atmosphere. In the case of N type, heating is performed at 500 ° C. for 2 hours. This environment is performed in a clean room that does not contaminate the wafer. The silicon wafer may be heated in a heat treatment furnace instead of the hot plate. In this case, in the atmosphere, N 2 / O 2 or Ar
/ O 2 atmosphere.
【００１４】この熱処理後、バルク中のほとんどのＣｕ
は表裏面側へそれぞれ移動する。特に、８０％以上のＣ
ｕがウェーハ表面側に移動する。このＣｕは、表面側は
そのままＴＸＲＦで分析可能である。また、ウェーハ表
面にＨＦ（２％）またはＨＦ（２％）／Ｈ2Ｏ2（２％）
混合溶液を滴下（１００〜２００μｌ）して全面に沿っ
て動かす。そして、このようにして回収液でＣｕをウェ
ーハ表面から回収すれば、回収後ＴＸＲＦ，ＡＡＳで容
易に分析が可能である。また、裏面側のＣｕも併せて回
収して分析すれば、シリコンウェーハ中のＣｕの総量を
測定することができる。なお、ウェーハ表面の洗浄・回
収では、上記ＨＦ溶液・ＨＦ／Ｈ2Ｏ2溶液に代えて、Ｈ
Ｃｌ溶液・ＨＣｌ／Ｈ2Ｏ2溶液・ＨＣｌ／ＨＦ溶液・Ｓ
Ｃ１溶液・Ｈ2ＳＯ4／Ｈ2Ｏ2溶液等を用いることができ
る。After this heat treatment, most of the Cu in the bulk is
Move to the front and back sides respectively. Especially 80% or more of C
u moves to the front surface side of the wafer. This Cu can be analyzed by TXRF on the surface side as it is. HF (2%) or HF (2%) / H 2 O 2 (2%) on the wafer surface
The mixed solution is dropped (100 to 200 μl) and moved along the entire surface. Then, if Cu is recovered from the wafer surface with the recovering liquid in this way, it is possible to easily analyze by TXRF and AAS after recovery. Further, if Cu on the back surface side is also collected and analyzed, the total amount of Cu in the silicon wafer can be measured. In the cleaning and recovery of the wafer surface, instead of the above HF solution and HF / H 2 O 2 solution, H
Cl solution, HCl / H 2 O 2 solution, HCl / HF solution, S
A C1 solution / H 2 SO 4 / H 2 O 2 solution or the like can be used.
【００１５】図２に、ウェーハ表面に付着したＣｕの各
種回収液による回収率を示す。この図に示すように、上
記熱処理により、ウェーハ表面からのＣｕの回収率は飛
躍的に高められる。２％ＨＦ溶液でのウェーハ表面から
の回収の場合も、ＨＦ（２％）／Ｈ2Ｏ2（２％）溶液で
の回収の場合もいずれもＣｕの回収率は、未処理の場合
に比較して大幅に高められる。FIG. 2 shows the recovery rate of Cu deposited on the wafer surface by various recovery solutions. As shown in this figure, the heat treatment dramatically increases the recovery rate of Cu from the wafer surface. In both cases of recovery from the wafer surface with the 2% HF solution and recovery with the HF (2%) / H 2 O 2 (2%) solution, the Cu recovery rate is comparable to that of the untreated case. And greatly increased.
【００１６】図３には、Ｃｕ汚染を除去した清浄なシリ
コンウェーハの製造方法を示している。この図にも示す
ように、まず、酸化膜を除去し、低温（５００℃・１５
分）で加熱する。そして、例えばＳＣ１洗浄によりウェ
ーハ表面を洗浄する。FIG. 3 shows a method for producing a clean silicon wafer from which Cu contamination has been removed. As shown in this figure, first, the oxide film is removed, and the low temperature (500 ° C. 15
Min)). Then, the wafer surface is cleaned by SC1 cleaning, for example.
【００１７】下表には、再結合ライフタイムを示してい
る。これは、この発明に係るシリコンウェーハについて
の電気特性の改善結果を示すためのものである。この表
に示すように、熱処理によりシリコンウェーハのライフ
タイム（τR）は改善されている。ライフタイム測定は
例えば反射マイクロ波法等の公知の方法で行っている。The following table shows the recombination lifetimes. This is for showing the improvement result of the electrical characteristics of the silicon wafer according to the present invention. As shown in this table, the heat treatment improves the lifetime (τR) of the silicon wafer. The lifetime is measured by a known method such as a reflection microwave method.
【００１８】[0018]
【００１９】[0019]
【発明の効果】この発明では、シリコンウェーハ表面お
よびバルク中のＣｕ濃度を低減することができる。ま
た、シリコンウェーハの電気特性（酸化膜耐圧等）・結
晶特性を高めることができる。また、Ｃｕ汚染されたシ
リコンウェーハからＣｕをゲッタリングすることができ
る。Ｃｕ汚染の少ないシリコンウェーハを製造すること
ができる。According to the present invention, the Cu concentration on the surface of the silicon wafer and in the bulk can be reduced. Also, the electrical characteristics (oxide film breakdown voltage, etc.) and crystal characteristics of the silicon wafer can be improved. Further, Cu can be gettered from a silicon wafer contaminated with Cu. A silicon wafer with less Cu contamination can be manufactured.
【図１】この発明の一実施例に係るシリコンウェーハの
Ｃｕ濃度の分析方法を示す工程図である。FIG. 1 is a process chart showing a method for analyzing Cu concentration in a silicon wafer according to an embodiment of the present invention.
【図２】この発明の一実施例に係るＣｕの回収率の向上
結果を示すグラフである。FIG. 2 is a graph showing an improvement result of a Cu recovery rate according to an example of the present invention.
【図３】この発明の一実施例に係るシリコンウェーハの
製造方法を示すフローチャートである。FIG. 3 is a flowchart showing a method for manufacturing a silicon wafer according to an embodiment of the present invention.
【手続補正書】[Procedure amendment]
【提出日】平成７年１０月３日[Submission date] October 3, 1995
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１７[Correction target item name] 0017
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１７】下表には、再結合ライフタイムを示してい
る。これは、この発明に係るシリコンウェーハについて
の電気特性の改善結果を示すためのものである。この表
に示すように、熱処理によりシリコンウェーハのライフ
タイム（τＲ）は改善されている。ライフタイム測定
は、例えば反射マイクロ波法等の公知の方法で行ってい
る。The following table shows the recombination lifetimes. This is for showing the improvement result of the electrical characteristics of the silicon wafer according to the present invention. As shown in this table, the lifetime (τR) of the silicon wafer is improved by the heat treatment. The lifetime is measured by a known method such as a reflection microwave method.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１８[Correction target item name] 0018
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１８】[0018]
【表】 【table】
Claims (3)
理した後、その表面を洗浄したシリコンウェーハ。1. A silicon wafer obtained by heat-treating a silicon wafer at 600 ° C. or lower and cleaning the surface thereof.
１×１０9個／ｃｍ2以下である請求項１に記載のシリコ
ンウェーハ。2. The silicon wafer according to claim 1, wherein the Cu concentration on the surface of the silicon wafer is 1 × 10 9 pieces / cm 2 or less.
で熱処理する工程と、この後シリコンウェーハ表面を洗
浄する工程と、を備えたシリコンウェーハの製造方法。3. A method of manufacturing a silicon wafer, comprising: a step of heat-treating the silicon wafer at a temperature of 600 ° C. or lower; and a step of cleaning the surface of the silicon wafer thereafter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24357595A JP3575644B2 (en) | 1995-08-28 | 1995-08-28 | Silicon wafer manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24357595A JP3575644B2 (en) | 1995-08-28 | 1995-08-28 | Silicon wafer manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0964052A true JPH0964052A (en) | 1997-03-07 |
| JP3575644B2 JP3575644B2 (en) | 2004-10-13 |
Family
ID=17105876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24357595A Expired - Fee Related JP3575644B2 (en) | 1995-08-28 | 1995-08-28 | Silicon wafer manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3575644B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000349025A (en) * | 1999-03-26 | 2000-12-15 | Semiconductor Energy Lab Co Ltd | Manufacture of semiconductor device |
| US6337235B1 (en) * | 1999-03-26 | 2002-01-08 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and manufacturing method thereof |
| EP1521296A2 (en) * | 2003-10-03 | 2005-04-06 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Method of reclaiming silicon wafers |
| US7601541B2 (en) * | 2003-05-12 | 2009-10-13 | Sumco Corporation | Method for detecting Cu concentration of silicon substrate |
| JP2010034444A (en) * | 2008-07-31 | 2010-02-12 | Sumco Corp | Method of manufacturing regenerated silicon wafer |
| CN103063692A (en) * | 2012-12-31 | 2013-04-24 | 上海申和热磁电子有限公司 | Roasting method and detection method for heavy metal in silicon wafer |
| US20140103492A1 (en) * | 2011-06-20 | 2014-04-17 | Shin-Etsu Handotai Co., Ltd. | Silicon wafer and method for producing the same |
| US20150187637A1 (en) * | 2013-12-30 | 2015-07-02 | Samsung Display Co., Ltd. | Manufacturing method for display device |
-
1995
- 1995-08-28 JP JP24357595A patent/JP3575644B2/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6337235B1 (en) * | 1999-03-26 | 2002-01-08 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device and manufacturing method thereof |
| JP2000349025A (en) * | 1999-03-26 | 2000-12-15 | Semiconductor Energy Lab Co Ltd | Manufacture of semiconductor device |
| US7601541B2 (en) * | 2003-05-12 | 2009-10-13 | Sumco Corporation | Method for detecting Cu concentration of silicon substrate |
| DE102004023425B4 (en) * | 2003-05-12 | 2017-08-24 | Sumco Corp. | Method for detecting the Cu concentration of a silicon substrate |
| US7699997B2 (en) | 2003-10-03 | 2010-04-20 | Kobe Steel, Ltd. | Method of reclaiming silicon wafers |
| EP1521296A3 (en) * | 2003-10-03 | 2006-01-18 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Method of reclaiming silicon wafers |
| EP1521296A2 (en) * | 2003-10-03 | 2005-04-06 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Method of reclaiming silicon wafers |
| JP2010034444A (en) * | 2008-07-31 | 2010-02-12 | Sumco Corp | Method of manufacturing regenerated silicon wafer |
| US20140103492A1 (en) * | 2011-06-20 | 2014-04-17 | Shin-Etsu Handotai Co., Ltd. | Silicon wafer and method for producing the same |
| US9337013B2 (en) | 2011-06-20 | 2016-05-10 | Shin-Etsu Handotai Co., Ltd. | Silicon wafer and method for producing the same |
| CN103063692A (en) * | 2012-12-31 | 2013-04-24 | 上海申和热磁电子有限公司 | Roasting method and detection method for heavy metal in silicon wafer |
| US20150187637A1 (en) * | 2013-12-30 | 2015-07-02 | Samsung Display Co., Ltd. | Manufacturing method for display device |
| US9362159B2 (en) * | 2013-12-30 | 2016-06-07 | Samsung Display Co., Ltd. | Manufacturing method for display device |
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