JPH03228327A - Cleaning method of semiconductor wafer - Google Patents
Cleaning method of semiconductor waferInfo
- Publication number
- JPH03228327A JPH03228327A JP2366390A JP2366390A JPH03228327A JP H03228327 A JPH03228327 A JP H03228327A JP 2366390 A JP2366390 A JP 2366390A JP 2366390 A JP2366390 A JP 2366390A JP H03228327 A JPH03228327 A JP H03228327A
- Authority
- JP
- Japan
- Prior art keywords
- cleaning
- water
- hydrochloric acid
- hydrofluoric acid
- mixed chemical
- 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
- 238000004140 cleaning Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000004065 semiconductor Substances 0.000 title claims abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910001868 water Inorganic materials 0.000 claims abstract description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 16
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 11
- 238000011109 contamination Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 235000012431 wafers Nutrition 0.000 description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 18
- 229910052710 silicon Inorganic materials 0.000 description 18
- 239000010703 silicon Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Cleaning By Liquid Or Steam (AREA)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は半導体ウェーハの洗浄方法に関し、特に重金属
汚染を除去するための半導体ウェーハの洗浄方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for cleaning semiconductor wafers, and more particularly to a method for cleaning semiconductor wafers to remove heavy metal contamination.
従来、半導体ウェーハ(以下単にウェーハという)の洗
浄方法としては、塩酸と過酸化水素と水を混合させて5
0〜70℃付近の液温とし、その中にウェーハを浸漬さ
せて洗浄する方法(以下HCρ7/H2O2/′H20
C性7いう)や、硫酸と過酸化水素とを混合させて80
〜130℃付近の液温で洗浄する方法(以下H2SO4
/H2O2洗浄という)や、希フッ酸を用いて常温で洗
浄する方法(以下DHF洗浄という)などが知られてお
り、一般に広く使用されている。Traditionally, semiconductor wafers (hereinafter simply referred to as wafers) have been cleaned by mixing hydrochloric acid, hydrogen peroxide, and water.
A method of cleaning by immersing the wafer in the liquid at a temperature of around 0 to 70°C (hereinafter referred to as HCρ7/H2O2/'H20)
7) or by mixing sulfuric acid and hydrogen peroxide.
A method of cleaning with liquid temperature around ~130℃ (hereinafter referred to as H2SO4
/H2O2 cleaning) and a method of cleaning at room temperature using dilute hydrofluoric acid (hereinafter referred to as DHF cleaning) are known and widely used.
上述した従来のウェーハの洗浄方法のうち、DHF洗浄
では、シリコン上の自然酸化膜はエツチング除去できる
という効果があるが、逆にシリコン表面が活性化される
ため、パーティクルが付着しやすいという欠点がある。Among the conventional wafer cleaning methods mentioned above, DHF cleaning has the effect of etching away the natural oxide film on silicon, but conversely it activates the silicon surface, so it has the disadvantage that particles tend to adhere to it. be.
また、重金属の除去性能については、Aρ、Fe、Ni
等シリコンよりイオン化傾向が大きい元素については除
去可能であるが、Cu等シリコンよりイオン化傾向が小
さい元素については除去性能が小さい。In addition, regarding the removal performance of heavy metals, Aρ, Fe, Ni
It is possible to remove elements that have a greater ionization tendency than silicon, such as Cu, but the removal performance is poor for elements that have a smaller ionization tendency than silicon, such as Cu.
次に、H2SO4/H2O2洗浄では、汚染金属のイオ
ン化傾向にかかわらず、重金属の除去性能は高いという
効果があるが、通常100℃以上の高温で用いるため、
自然酸化膜が形成されやすいという欠点がある。Next, H2SO4/H2O2 cleaning has the effect of high removal performance of heavy metals regardless of the ionization tendency of contaminant metals, but since it is usually used at high temperatures of 100°C or higher,
There is a drawback that a natural oxide film is easily formed.
同様にI(CI 、、” H202,7/H20洗浄で
は、重金属の除去性能は高いという効果があるか、70
°C前後で用いるため自然酸化膜が形成される点や、H
Cρか腐蝕性か高いので、洗浄装置の部品を腐蝕する等
の欠点がある。Similarly, I (CI,,"H202,7/H20 cleaning has the effect of high removal performance of heavy metals, 70
Since it is used at around °C, a natural oxide film is formed, and H
Since Cρ is highly corrosive, it has drawbacks such as corroding parts of cleaning equipment.
本発明の半導体ウェーハの洗浄方法は、フ・・ノ酸と塩
酸と水との混合薬液またはフッ酸と塩酸と過酸化水素と
水との混合薬液中に常温で半導体ウェーハを浸漬するも
のである。The semiconductor wafer cleaning method of the present invention involves immersing the semiconductor wafer at room temperature in a mixed chemical solution of hydrofluoric acid, hydrochloric acid, and water or a mixed chemical solution of hydrofluoric acid, hydrochloric acid, hydrogen peroxide, and water. .
次に本発明について図面を参照して説明する。 Next, the present invention will be explained with reference to the drawings.
本発明の実施例1として、フッ酸と塩酸と水の混合比を
それぞれ1対10対100の混合薬液を作り常温で用い
る。更に本発明の実施例2として、フッ酸と塩酸と過酸
化水素水と水との混合比をそれぞれ1対10対20対1
00の混合薬液を作り常温で用いる。As Example 1 of the present invention, a mixed chemical solution with a mixing ratio of hydrofluoric acid, hydrochloric acid, and water of 1:10:100, respectively, is prepared and used at room temperature. Furthermore, as Example 2 of the present invention, the mixing ratio of hydrofluoric acid, hydrochloric acid, hydrogen peroxide solution, and water was 1:10:20:1, respectively.
00 mixed chemical solution is prepared and used at room temperature.
第1図は本発明の実施例1と実施例2の洗浄方法および
従来の技術を用いた洗浄方法を行った場合のシリコンウ
ェーハ表面の残留重金属濃度を指数で表した実験結果で
ある。FIG. 1 shows experimental results in which the concentration of residual heavy metals on the surface of a silicon wafer is expressed as an index when the cleaning methods of Examples 1 and 2 of the present invention and the cleaning method using a conventional technique are performed.
シリコンウェーハ表面を予めFeおよびCuで100p
pbの濃度で定量的に汚染させておく。The surface of the silicon wafer is coated with 100p of Fe and Cu in advance.
Quantitative contamination with PB concentration.
その後本発明の実施例1,2の洗浄方法および比較のた
めに従来の技術としてHCρ/H2O2/H20(1:
1:5)混合液を70°Cで用いて洗浄する方法とHF
/H2O(1: 100)混合液を常温で用いて洗浄す
る方法とを各5分間行った後、シリコンウェーハ表面の
残留重金属濃度を測定し、指数で示した。After that, HCρ/H2O2/H20 (1:
1:5) Method of cleaning using mixed solution at 70°C and HF
/H2O (1:100) mixed solution at room temperature for 5 minutes each, the residual heavy metal concentration on the silicon wafer surface was measured and expressed as an index.
Feについては残留濃度は各洗浄方法にかかわらす除去
効果が高く、定量汚染を行なわなかったレベルまで除去
されていることがわかる。Cuについては、HF /
H20洗浄は残留重金属濃度か高く除去効果が小さいが
、実施例1.2およびHC!2./H20゜、/’H2
0洗浄では除去効果が大きい。Regarding Fe, it can be seen that the removal effect of each cleaning method was high, and the residual concentration was removed to a level where quantitative contamination was not performed. For Cu, HF/
Although H20 cleaning has a high residual heavy metal concentration and a small removal effect, Example 1.2 and HC! 2. /H20°, /'H2
Zero cleaning has a large removal effect.
第2図は、本発明の実施例1と実施例2の洗浄方法およ
び従来の技術を用いた洗浄方法を行った後のシリコンウ
ェーハ表面の自然酸化膜厚を指数で表した実験結果であ
る。FIG. 2 shows experimental results in which the natural oxide film thickness on the surface of a silicon wafer is expressed as an index after performing the cleaning methods of Examples 1 and 2 of the present invention and the cleaning method using the conventional technology.
シリコンウェーハ上の自然酸化膜を予めフッ酸対水の混
合比が1対200の希フッ酸溶液でエツチング除去し、
水洗後乾燥させる。このシリコンウェーハ上の自然酸化
膜厚をエリプソメーターで測定した結果、すべてのシリ
コンウェーハで自然酸化膜厚は7Å以下であることを確
認した。以上のシリコンウェーハを本発明の実施例1と
実施例2の洗浄方法および従来の技術を用いた洗浄方法
とを各10分間行った後のシリコンウェーハ上の自然酸
化膜厚をエリプソメーターで測定し、膜厚を指数で示し
た。The natural oxide film on the silicon wafer is removed by etching in advance with a dilute hydrofluoric acid solution with a mixture ratio of hydrofluoric acid and water of 1:200.
Dry after washing with water. As a result of measuring the natural oxide film thickness on these silicon wafers with an ellipsometer, it was confirmed that the natural oxide film thickness on all silicon wafers was 7 Å or less. The natural oxide film thickness on the silicon wafers was measured using an ellipsometer after the above silicon wafers were subjected to the cleaning methods of Examples 1 and 2 of the present invention and the cleaning method using conventional technology for 10 minutes each. , the film thickness is expressed as an index.
従来技術の洗浄方法のうち、HCρ/H2O2/H20
洗浄を施したシリコンウェーハについては、洗浄によっ
て形成される自然酸化膜厚が厚いことがわかる。これに
対して本発明の実施例1゜実施例2の洗浄方法およびD
HF洗浄を施したシリコンウェーハについては、洗浄に
よって形成される自然酸化膜厚は非常に小さいことがわ
かる。Among the conventional cleaning methods, HCρ/H2O2/H20
It can be seen that the silicon wafer that has been cleaned has a thick natural oxide film formed by cleaning. In contrast, Example 1 of the present invention, the cleaning method of Example 2, and D
It can be seen that for silicon wafers that have been subjected to HF cleaning, the thickness of the natural oxide film formed by cleaning is extremely small.
第3図は本発明の実施例1と実施例2の洗浄方法および
従来の技術を用いて洗浄方法を行った後のシリコンウェ
ーハ表面のパーティクル付着数を指数で表した実験結果
である。シリコン上のパーティクル数はレーザー光散乱
検出法を用いたパーティクルカウンターで測定した。FIG. 3 shows experimental results in which the number of particles attached to the silicon wafer surface is expressed as an index after the cleaning methods of Examples 1 and 2 of the present invention and the conventional technique were used. The number of particles on silicon was measured with a particle counter using laser light scattering detection method.
第3図から明らかなように、DHF洗浄を施したウェー
ハ上のパーティクル付着数が多い。これに対して、本発
明の実施例ではパーティクル付着数が少なく、特に実施
例2の洗浄を施したウェーハ上のパーティクル付着数は
非常に少ない。これはフッ酸/塩酸/過酸化水素/水の
混合液中で、希フッ酸にて自然酸化膜をエツチング除去
することによって極めて活性なシリコン表面が露出する
が、同時に塩酸および過酸化水素によってシリコン表面
の活性化を抑制した効果と考えられる。As is clear from FIG. 3, a large number of particles adhere to the wafer that has been subjected to DHF cleaning. On the other hand, in the examples of the present invention, the number of attached particles is small, and in particular, the number of attached particles on the wafer that has been cleaned in Example 2 is very small. This is done by etching away the native oxide film with dilute hydrofluoric acid in a mixed solution of hydrofluoric acid/hydrochloric acid/hydrogen peroxide/water, exposing the extremely active silicon surface. This is thought to be an effect of suppressing surface activation.
以上説明したように本発明は、半導体ウエーハの洗浄方
法として、フッ酸と塩酸と水又はフッ酸と塩酸と過酸(
ヒ水素と水とを混きさせた薬液を常温て用いることによ
り、重金属汚染の除去性能は金属のイオン化傾向に依ら
ず大きく、また常温でフッ酸を含む薬液で洗浄するので
洗浄によって形成される自然酸化膜厚も小さくなる。更
に、フッ酸と塩酸と過酸化水素と水との混合液て洗浄を
行う場合には特に付着するパーティクル数は少なくなる
。As explained above, the present invention uses hydrofluoric acid, hydrochloric acid and water, or hydrofluoric acid, hydrochloric acid and peracid (
By using a chemical mixture of arsenic and water at room temperature, the removal performance of heavy metal contamination is large regardless of the ionization tendency of the metal, and since it is cleaned with a chemical solution containing hydrofluoric acid at room temperature, it is possible to remove heavy metal contamination by cleaning. The natural oxide film thickness also becomes smaller. Furthermore, when cleaning is performed with a mixed solution of hydrofluoric acid, hydrochloric acid, hydrogen peroxide, and water, the number of attached particles is particularly reduced.
また従来、塩酸を含む薬液を70’C前後まで加温して
洗浄する場合は、塩酸と蒸気等によって洗浄装置の部品
か腐蝕する場合か多かったか、本発明の洗浄方法ては薬
液を常温で用いるので、洗浄装置への悪影響も少ない。In addition, conventionally, when cleaning a chemical solution containing hydrochloric acid by heating it to around 70'C, the hydrochloric acid and steam often corrode parts of the cleaning equipment. Since it is used, there is little negative impact on the cleaning equipment.
加えて、従来、DHF洗浄とHCρ/H2O2/H20
洗浄を併用することが多かったか、本発明では一種類の
薬液を用いた洗浄方法で2種類の洗浄方法を併用して連
続処理した場合と同等以上の効果か得られるため、洗浄
装置を小さくすることかできる。このように本発明を用
いれば上述のような効果を得ることができる。In addition, conventionally, DHF cleaning and HCρ/H2O2/H20
Perhaps cleaning is often used in combination, but in the present invention, a cleaning method using one type of chemical solution is as effective as or better than continuous processing using two types of cleaning methods, so the cleaning device is made smaller. I can do it. By using the present invention in this manner, the effects described above can be obtained.
第1図〜第3図は本発明の実施例と従来例との洗浄効果
を説明するための重金属濃度、酸化膜厚及びパーティク
ル付着数を示す図である。FIGS. 1 to 3 are diagrams showing the heavy metal concentration, oxide film thickness, and number of attached particles for explaining the cleaning effects of the embodiment of the present invention and the conventional example.
Claims (1)
酸化水素と水との混合薬液中に常温で半導体ウェーハを
浸漬することを特徴とする半導体ウェーハの洗浄方法。A method for cleaning a semiconductor wafer, comprising immersing the semiconductor wafer in a mixed chemical solution of hydrofluoric acid, hydrochloric acid, and water or a mixed chemical solution of hydrofluoric acid, hydrochloric acid, hydrogen peroxide, and water at room temperature.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2366390A JP2841627B2 (en) | 1990-02-02 | 1990-02-02 | Semiconductor wafer cleaning method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2366390A JP2841627B2 (en) | 1990-02-02 | 1990-02-02 | Semiconductor wafer cleaning method |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH03228327A true JPH03228327A (en) | 1991-10-09 |
JP2841627B2 JP2841627B2 (en) | 1998-12-24 |
Family
ID=12116734
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2366390A Expired - Lifetime JP2841627B2 (en) | 1990-02-02 | 1990-02-02 | Semiconductor wafer cleaning method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2841627B2 (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995016277A1 (en) * | 1993-12-10 | 1995-06-15 | Tadahiro Ohmi | Surface cleaning method and surface cleaning agent of substrate |
US5560857A (en) * | 1993-10-19 | 1996-10-01 | Nippon Steel Corporation | Solution for cleaning silicon semiconductors and silicon oxides |
EP0936268A3 (en) * | 1998-01-16 | 1999-09-15 | Kurita Water Industries Ltd. | Cleaning solution for electromaterials and method for using the same |
US6214129B1 (en) * | 1997-12-29 | 2001-04-10 | Yasuyuki Nakaoka | Cleaning method with hydrochloric acid-hydrogen peroxide mixture |
JP2001144083A (en) * | 1999-11-11 | 2001-05-25 | Nec Corp | Solution and method for recovering platinum group impurities |
US6245650B1 (en) | 1999-01-28 | 2001-06-12 | Nec Corporation | Process for production of semiconductor device |
US6432836B1 (en) * | 1998-09-17 | 2002-08-13 | Nec Corporation | Cleaning method for semiconductor substrate and cleaning solution |
US6727187B2 (en) | 2000-04-27 | 2004-04-27 | Renesas Technology Corp. | Fabrication method for semiconductor device |
CN102728573A (en) * | 2012-06-19 | 2012-10-17 | 天威新能源控股有限公司 | Process for cleaning damage layer of reactive ion etching (RIE) flocking surface of crystalline silicon |
CN104560461A (en) * | 2015-02-24 | 2015-04-29 | 烟台顺隆化工科技有限公司 | Washing agent for mercury-polluted building wastes |
CN106409977A (en) * | 2016-11-21 | 2017-02-15 | 新奥光伏能源有限公司 | Solar cell silicon wafer cleaning method and solar cell preparation method |
CN106910674A (en) * | 2017-03-02 | 2017-06-30 | 东莞市天域半导体科技有限公司 | A kind of cleaning method for removing SiC epitaxial wafer metallic pollution or residual |
CN114082740A (en) * | 2022-01-19 | 2022-02-25 | 北京通美晶体技术股份有限公司 | Method for cleaning germanium wafer and application thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101817006A (en) * | 2010-03-22 | 2010-09-01 | 浙江矽盛电子有限公司 | Method for cleaning surface of solar silicon wafer |
-
1990
- 1990-02-02 JP JP2366390A patent/JP2841627B2/en not_active Expired - Lifetime
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5560857A (en) * | 1993-10-19 | 1996-10-01 | Nippon Steel Corporation | Solution for cleaning silicon semiconductors and silicon oxides |
WO1995016277A1 (en) * | 1993-12-10 | 1995-06-15 | Tadahiro Ohmi | Surface cleaning method and surface cleaning agent of substrate |
US6214129B1 (en) * | 1997-12-29 | 2001-04-10 | Yasuyuki Nakaoka | Cleaning method with hydrochloric acid-hydrogen peroxide mixture |
KR100437429B1 (en) * | 1998-01-16 | 2004-06-25 | 쿠리타 고교 가부시키가이샤 | Cleaning water for electronic material and cleaning method of electronic material |
EP0936268A3 (en) * | 1998-01-16 | 1999-09-15 | Kurita Water Industries Ltd. | Cleaning solution for electromaterials and method for using the same |
US6346505B1 (en) | 1998-01-16 | 2002-02-12 | Kurita Water Industries, Ltd. | Cleaning solution for electromaterials and method for using same |
US6432836B1 (en) * | 1998-09-17 | 2002-08-13 | Nec Corporation | Cleaning method for semiconductor substrate and cleaning solution |
US6245650B1 (en) | 1999-01-28 | 2001-06-12 | Nec Corporation | Process for production of semiconductor device |
JP2001144083A (en) * | 1999-11-11 | 2001-05-25 | Nec Corp | Solution and method for recovering platinum group impurities |
US6727187B2 (en) | 2000-04-27 | 2004-04-27 | Renesas Technology Corp. | Fabrication method for semiconductor device |
CN102728573A (en) * | 2012-06-19 | 2012-10-17 | 天威新能源控股有限公司 | Process for cleaning damage layer of reactive ion etching (RIE) flocking surface of crystalline silicon |
CN104560461A (en) * | 2015-02-24 | 2015-04-29 | 烟台顺隆化工科技有限公司 | Washing agent for mercury-polluted building wastes |
CN106409977A (en) * | 2016-11-21 | 2017-02-15 | 新奥光伏能源有限公司 | Solar cell silicon wafer cleaning method and solar cell preparation method |
CN106910674A (en) * | 2017-03-02 | 2017-06-30 | 东莞市天域半导体科技有限公司 | A kind of cleaning method for removing SiC epitaxial wafer metallic pollution or residual |
CN114082740A (en) * | 2022-01-19 | 2022-02-25 | 北京通美晶体技术股份有限公司 | Method for cleaning germanium wafer and application thereof |
CN114082740B (en) * | 2022-01-19 | 2022-04-08 | 北京通美晶体技术股份有限公司 | Method for cleaning germanium wafer and application thereof |
Also Published As
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---|---|
JP2841627B2 (en) | 1998-12-24 |
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