KR100646730B1 - Etching solution for evaluating crystral faults in silicone wafer and evaluation method using the same - Google Patents

Etching solution for evaluating crystral faults in silicone wafer and evaluation method using the same Download PDF

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KR100646730B1
KR100646730B1 KR1020040115528A KR20040115528A KR100646730B1 KR 100646730 B1 KR100646730 B1 KR 100646730B1 KR 1020040115528 A KR1020040115528 A KR 1020040115528A KR 20040115528 A KR20040115528 A KR 20040115528A KR 100646730 B1 KR100646730 B1 KR 100646730B1
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corrosion
evaluating
crystal defects
defects
corrosion solution
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KR20060076904A (en
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이성욱
김영훈
박영창
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주식회사 실트론
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84Systems specially adapted for particular applications
    • G01N21/88Investigating the presence of flaws or contamination
    • G01N21/95Investigating the presence of flaws or contamination characterised by the material or shape of the object to be examined
    • G01N21/9501Semiconductor wafers
    • CCHEMISTRY; METALLURGY
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    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00Etching, surface-brightening or pickling compositions
    • C09K13/04Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound

Abstract

본 발명은 실리콘웨이퍼의 결정 결함 평가용 부식액, 더욱 자세하게는 HF, HNO3, CH3COOH, 및 H2O을 포함하는 실리콘웨이퍼(silicon Wafer)의 결정 결함 평가용 부식액에 관한 것으로서, 본 발명의 부식액은 2006년부터 규제 대상인 Cr을 함유하지 않고, 또한 종래 기술에서 사용한 Cu(NO3)2 및 AgNO3를 함유하지 않았으면서 빠르고 정확하게 결정 결함을 평가를 할 수 있어 실리콘웨이퍼의 결정 결함 평가에 유용하게 사용될 수 있다. The present invention relates to a corrosion solution for evaluating crystal defects of silicon wafers, and more particularly, to a corrosion defect for crystal defect evaluation of silicon wafers including HF, HNO 3 , CH 3 COOH, and H 2 O. Corrosion liquids do not contain regulated Cr since 2006, and do not contain Cu (NO 3 ) 2 and AgNO 3 used in the prior art, and can be used to evaluate crystal defects of silicon wafers quickly and accurately. Can be used.

실리콘웨이퍼, 결정 결함 평가, 부식액, 아세트산Silicon Wafer, Crystal Defect Evaluation, Corrosion Solution, Acetic Acid

Description

실리콘 웨이퍼의 결정 결함 평가용 부식액 및 이를 이용한 결정결함 평가방법{ETCHING SOLUTION FOR EVALUATING CRYSTRAL FAULTS IN SILICONE WAFER AND EVALUATION METHOD USING THE SAME}Etching solution for evaluating crystal defects of silicon wafers and methods for evaluating crystal defects using the same {{ETCHING SOLUTION FOR EVALUATING CRYSTRAL FAULTS IN SILICONE WAFER AND EVALUATION METHOD USING THE SAME}

도 1a는 본 발명의 실시예 1 및 비교예 1에 따라 수행된 OiSF 평가결과를 보여주는 사진이고,Figure 1a is a photograph showing the OiSF evaluation results performed according to Example 1 and Comparative Example 1 of the present invention,

도 1b는 본 발명의 실시예 1 및 비교예 1에 따라 수행된 OiSF 평가결과를 보여주는 그래프이고1B is a graph showing OiSF evaluation results performed according to Example 1 and Comparative Example 1 of the present invention.

도 1c는 본 발명의 실시예 1 및 비교예 1에 따라 수행된 OiSF 평가결과에 대한 회귀분석 결과를 나타낸다. Figure 1c shows the regression analysis results for the OiSF evaluation performed in accordance with Example 1 and Comparative Example 1 of the present invention.

도 2a는 본 발명의 실시예 2 및 비교예 2에 따라 수행된 OiSF 평가결과를 보여주는 사진이고,Figure 2a is a photograph showing the OiSF evaluation results performed in accordance with Example 2 and Comparative Example 2 of the present invention,

도 2b는 본 발명의 실시예 2 및 비교예 2에 따라 수행된 OiSF 평가결과를 보여주는 그래프이고2b is a graph showing OiSF evaluation results performed according to Example 2 and Comparative Example 2 of the present invention;

도 2c는 본 발명의 실시예 2 및 비교예 2에 따라 수행된 OiSF 평가결과에 대한 회귀분석 결과를 나타낸다. Figure 2c shows the regression analysis results for OiSF evaluation performed in accordance with Example 2 and Comparative Example 2 of the present invention.

본 발명은 웨이퍼의 결정 결함 평가용 부식제, HF, HNO3, CH3COOH, 및 H2O을 포함하는 실리콘웨이퍼(silicon Wafer)의 결정 결함 평가용 부식액에 관한 것으로서, 6가 Cr, Cu(NO3)2 및 AgNO3를 함유하지 않으면서 빠르고 정확하게 결정 결함을 평가하기 위한 부식제 및 이를 이용한 실리콘 웨이퍼의 결정결함 평가용 부식액에 관한 것이다. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a corrosion solution for evaluating crystal defects of silicon wafers including a corrosive agent for evaluating crystal defects of a wafer, HF, HNO 3 , CH 3 COOH, and H 2 O. 3 ) A corrosive agent for quickly and accurately evaluating crystal defects without containing 2 and AgNO 3 , and a corrosive liquid for crystal defect evaluation of a silicon wafer using the same.

실리콘 웨이퍼에는 결정 결함이 존재하고 이 결정 결함들은 장치에 나쁜 영향을 주기도 하고 금속 불순물을 게더링(Gettering)하는 데 중요한 역할을 하기도 한다. 따라서 이런 결함을 쉽고 빠르게 평가하는 기술은 아주 중요하다. 일반적으로 웨이퍼는 중심에서 가장자리까지 COP, FPD, OiSF, BMD, LDP의 품질특성(결정결함)이 순차적으로 나타나고 있으며, 이는 소자 수율 및 품질에 영향을 미치는 것으로 확인되고 있다. 반도체소자의 고집적화기술이 발달됨에 따라, 실리콘웨이퍼에서의 미세결함제어는 상당히 중요한 기술적과제중의 하나가되었다. 결정결함을 완전히 제거시킴과 동시에 웨이퍼 중심에서 가장자리까지 품질 균일도를 대폭 개선해야 한다. Crystal wafers are present in silicon wafers, and these crystal defects may adversely affect the device and may play an important role in gathering metal impurities. Therefore, the technique of evaluating these defects easily and quickly is very important. In general, the wafers have the quality characteristics (defects) of COP, FPD, OiSF, BMD, and LDP sequentially from the center to the edge, which are confirmed to affect device yield and quality. As the high integration technology of semiconductor devices has been developed, fine defect control in silicon wafers has become one of the important technical challenges. The quality uniformity from the center of the wafer to the edge must be greatly improved while the crystal defects are completely removed.

웨이퍼의 결정 결함을 평가하기 위한 종래에 알려진 방법으로는, 선택적 습식 에칭법으로 결함을 표면화하고, 현미경을 이용한 평가방법이 있다. 결정 결함 평가용 습식 부식으로는 주로 산화제와 플루오르화 수소산의 혼합물에 의한 부식법이 사용되며 이때 부식반응은 산화제에 의한 실리콘의 산화와 플루오르화수소산에 의한 산화규소의 용해로 이루어진다. 결정 결함 평가용 선택적 부식제로 사용하는 것으로는 하기 표 1과 같다(일본 특허공개공보 2002-236081).As a conventionally known method for evaluating crystal defects of a wafer, there is an evaluation method in which a defect is surfaced by a selective wet etching method and a microscope is used. The wet corrosion for the determination of crystal defects is mainly the corrosion method by the mixture of oxidizing agent and hydrofluoric acid, where the corrosion reaction consists of oxidation of silicon by oxidizing agent and dissolution of silicon oxide by hydrofluoric acid. Use as a selective corrosion agent for evaluation of crystal defects is shown in Table 1 below (Japanese Patent Laid-Open No. 2002-236081).

부식액Corrosion 조성Furtherance 에칭속도Etching speed dashdash HF, HNO3, CH3CHOOH (1:3:12)HF, HNO 3 , CH 3 CHOOH (1: 3: 12) ~0.2㎛/min~ 0.2㎛ / min SirtleSirtle HF, Cr, H2O(1:0.4:0.2)HF, Cr, H2O (1: 0.4: 0.2) ~1㎛/min~ 1㎛ / min SeccoSecco HF, K2Cr2O7수용액(0.15mol%) (2:1)HF, aqueous K 2 Cr 2 O 7 solution (0.15 mol%) (2: 1) ~1.2㎛/min~ 1.2㎛ / min WrightWright HF, HNO3, CrO3수용액(5mol%). Cu(NO3)2, CH3COOH, H2OHF, HNO 3 , CrO 3 aqueous solution (5 mol%). Cu (NO 3 ) 2 , CH 3 COOH, H 2 O ~1㎛/min~ 1㎛ / min

상기 표에 나타낸 바와 같이, Dash부식액은 산화제로서 질산을 사용하고 6가 크롬을 포함하지 않으며, HF: HNO3: CH3COOH가 1: 3: 12의 부피비 조성되어 있고 결정의 면방위에 관계없이 검출될 수 있으나 부식속도가 낮아 부식을 장시간(약 30분)시켜야 하는 단점이 있다. 상기 Dash부식액의 단점을 개선한 것으로서, Sirtle 부식액은 모든 결정면에 적용할 수 없어 그 사용대상이 제한되고, Secco 부식액은 부식속도는 빠르나 거품이 달라붙기 쉽기 때문에 초음파세척을 행할 필요가 있으며, Wright 부식액은 부식속도, 적용대상 등이 장점으로 널리 사용되고 있다.As shown in the table above, the Dash corrosion solution uses nitric acid as the oxidizing agent and does not contain hexavalent chromium, and has a volume ratio of HF: HNO 3 : CH 3 COOH 1: 3: 12 and regardless of the orientation of the crystals. Although it can be detected, there is a disadvantage that the corrosion rate is low and the corrosion must be long (about 30 minutes). As the improvement of the drawback of the Dash corrosion solution, Sirtle corrosion solution is not applicable to all crystal surfaces, its use is limited, and Secco corrosion solution needs to be ultrasonically cleaned because the corrosion rate is fast but the foam is easy to stick. Silver is widely used for its advantages such as corrosion rate and application.

그러나, 상기 Sirtle 부식액, Wright 부식액, 및 Secco 부식액은 산화제로서 6가 크롬을 사용하고 있다. 6가 크롬은 환경 유해 물질로서 사용이 규제됨으로써 대체 부식액이 개발이 절실하다. However, the Sirtle corrosion solution, Wright corrosion solution, and Secco corrosion solution use hexavalent chromium as the oxidizing agent. Hexavalent chromium has been regulated as an environmentally hazardous substance, requiring the development of alternative corrosion solutions.

실리콘웨이퍼의 결정 결함 평가용으로서 6가 Cr을 함유하지 않은 부식액에 대한 것으로는 미국특허 제4,787,997호에는 HF, HNO3, CH3COOH 혼합용액에 Cu(NO3 )2, AgNO3등이 첨가된 에칭 용액으로 실리콘웨이퍼의 결정 결함을 평가할 수 있으나 Cu(NO3)2와 AgNO3를 첨가하지 않으면 OiSF나 BMD를 평가하기가 어렵다는 문제점이 있다. US Pat. No. 4,787,997 discloses that Cu (NO 3 ) 2 , AgNO 3, etc. are added to HF, HNO 3 , CH 3 COOH mixed solution for the evaluation of crystalline defects of silicon wafers. Although it is possible to evaluate crystal defects of silicon wafers with an etching solution, it is difficult to evaluate OiSF or BMD without adding Cu (NO 3 ) 2 and AgNO 3 .

따라서, 환경에 유해한 6가 크롬을 함유하지 않으면서 단시간내에 효율적으로 실리콘 웨이퍼의 결정 결함을 평가하기 위한 부식제가 필요한 실정이다.Therefore, there is a need for a corrosive agent for efficiently evaluating crystal defects of a silicon wafer in a short time without containing hexavalent chromium, which is harmful to the environment.

본 발명은 상기와 같은 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 환경에 유해한 6가 크롬을 함유하지 않으면서 단시간내에 효율적으로 실리콘웨이퍼의 결정 결함 평가용 부식액을 제공하는 데 있다.SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a corrosion solution for evaluating crystal defects of silicon wafers efficiently in a short time without containing hexavalent chromium harmful to the environment.

본 발명의 또다른 목적은 상기 결정 결함 평가용 부식액을 사용하여 정확하고 빠르게 실리콘웨이퍼의 결정 결함을 평가하는 방법을 제공하는 것이다. It is still another object of the present invention to provide a method for accurately and quickly evaluating crystal defects of silicon wafers using the above-described corrosion solution for crystal defect evaluation.

본 발명은 HF : HNO3 : CH3COOH : H2O = 0.5~1.5: 5 ~ 15 : 4~10 : 2~4 (부피비)로 포함하는, 실리콘웨이퍼(silicon Wafer)의 결정 결함 평가용 부식액에 관한 것이다. In the present invention, HF: HNO 3 : CH 3 COOH: H 2 O = 0.5 to 1.5: 5 to 15: 4 to 10: 2 to 4 (volume ratio), a corrosion solution for evaluating crystal defects of a silicon wafer (silicon wafer) It is about.

또한 본 발명은 HF : HNO3 : CH3COOH : H2O = 0.5~1.5: 5 ~ 15 : 4~10 : 2~4 (부피비)로 포함하는 부식액으로 실리콘웨이퍼(silicon Wafer)를 처리하고, 현미경으로 결정결함을 평가하는 실리콘 웨이퍼의 결정 결함 평가방법에 관한 것이다. In addition, the present invention is treated with silicon wafer (silicon wafer) with a corrosion solution containing HF: HNO 3 : CH 3 COOH: H 2 O = 0.5 ~ 1.5: 5 ~ 15: 4 ~ 10: 2 ~ 4 (volume ratio), A crystal defect evaluation method of a silicon wafer for evaluating crystal defects under a microscope.

본 발명에 따른 실리콘웨이퍼의 결정 결함 평가용 부식액은, 2006년부터 규제 대상인 Cr을 함유하지 않고, 또한 종래 기술에서 사용한 Cu(NO3)2나 AgNO3 를 함 유하지 않았으면서 빠르고 정확한 결정 결함을 평가를 할 수 있다. Corrosion fluid for the evaluation of crystal defects of silicon wafers according to the present invention is fast and accurate crystal defects without containing Cr, which is regulated since 2006, and does not contain Cu (NO 3 ) 2 or AgNO 3 used in the prior art. Can evaluate

이하 본 발명을 상세히 설명하고자 한다.Hereinafter, the present invention will be described in detail.

본 발명의 부식액은 실리콘웨이퍼의 결정 결함중 대표적인 결정 결함인 OiSF와 BMD에 대한 평가를 위한 것이다. The corrosion solution of the present invention is for evaluation of OiSF and BMD which are representative crystal defects among the crystal defects of silicon wafers.

본 발명에 따른 결정 결함 평가용 부식액은 49% HF : 70% HNO3 : 100% CH3COOH : H2O = 0.5~1.5: 5 ~ 15 : 4~10 : 2~4 (부피비)로 포함하며, 바람직하게는 하는, 49% HF : 70% HNO3 : 100% CH3COOH : H2O = 1: 9 ~ 11 : 6 ~ 8 : 2 ~4 (부피비)이다. 상기 조성비를 벗어날 경우에는 부식이 과도하게 되거나 부식이 약하게 되는데 이를 경우에는 OiSF나 BMD 같은 결함의 밀도가 기존의 Wright 부식액을 사용했을 때보다 정확도가 떨어진다는 문제가 있다. 본 발명에 따른 부식액을 사용하는 경우에는 종래의 Dash 부식액에 비해 부식속도가 휠씬 빨라, 단시간에 결정결함을 표면화하여 정확하게 평가할 수 있는 장점이 있다. Corrosion solution for crystal defect evaluation according to the present invention comprises 49% HF: 70% HNO 3 : 100% CH 3 COOH: H 2 O = 0.5 ~ 1.5: 5 ~ 15: 4 ~ 10: 2 ~ 4 (volume ratio) 49% HF: 70% HNO 3 : 100% CH 3 COOH: H 2 O = 1: 9-11: 6-8: 2-4 (volume ratio). If the composition ratio is out of the corrosion is excessive or the corrosion is weak in this case there is a problem that the density of defects such as OiSF or BMD is less accurate than when using the conventional Wright corrosion solution. When the corrosion solution according to the present invention is used, the corrosion rate is much faster than that of the conventional Dash corrosion solution, and the surface of the crystal defects can be accurately evaluated in a short time.

또한 본 발명은 상기 실리콘 웨이퍼의 결정결함 평가용 부식액을 이용하여 실리콘웨이퍼(silicon Wafer)를 부식하여 결정결함을 표면화하고, 현미경으로 결함을 평가하는 것으로 포함하는 실리콘 웨이퍼의 결정 결함 평가방법에 관한 것이다. 상기 현미경을 이용한 결정결함 평가는 통상의 알려진 결정 결함 평가법을 사용할 수 있으며, 그 한예로는 부식처리후에 광학 현미경으로 결함 위치를 찾고 광학 현미경의 자동 결정결함계수 기능으로 결정 밀도를 평가할 수 있다. The present invention also relates to a method for evaluating crystal defects of a silicon wafer comprising corroding a silicon wafer using a corrosion defect for evaluating crystal defects of the silicon wafer to surface the crystal defects and evaluating the defects under a microscope. . The determination of crystal defects using the microscope can use a conventional known crystal defect evaluation method. For example, after the corrosion treatment, the defect position can be found by an optical microscope and the crystal density can be evaluated by the automatic crystal defect coefficient function of the optical microscope.

상기 부식액 처리는 3 분 내지 5분간 수행하는 것이다. 본 발명은 종래의 Dash부식액의 처리시간보다 월등히 빠르다. 상기 부식액의 처리는 25℃ 에서, 1 기압하에서 수행할 수 있다. 상기 부식액의 처리는 종래의 Wright 부식액의 처리와 달리 교반하지 않고 수행한다. The corrosive treatment is performed for 3 to 5 minutes. The present invention is much faster than the processing time of the conventional Dash corrosion solution. The treatment of the corrosion solution may be carried out at 25 ° C., under 1 atmosphere. The treatment of the corrosion solution is performed without stirring unlike the conventional treatment of Wright corrosion solution.

도 1a 내지 도 1c는 OiSF 열처리된 시료를 기존의 Wright 부식액과 본 발명에 따른 부식액으로 각각 부식한 후에 OiSF를 평가한 결과이다. 평가 결과 R-square가 90%로 본 발명의 부식액으로 OiSF를 평가하는 것이 가능함을 알 수 있다. Figures 1a to 1c is the result of evaluating OiSF after the OiSF heat-treated samples corrode each with the conventional Wright corrosion solution and the corrosion solution according to the present invention. The evaluation result shows that it is possible to evaluate OiSF with the corrosion solution of the present invention with an R-square of 90%.

도 2a 내지 2c는 정상적으로 2단계 열처리가 된 실리콘웨이퍼의 절단한 시료에 대해, 본 발명의 부식액과 Wright 부식액을 이용하여 BMD를 평가한 결과이다. 평가 결과 R-square가 98%로 본 발명의 부식액으로 부식시켜 BMD를 평가하는 것이 가능하며 따라서 6가 크롬을 포함하는 기존의 부식액을 대체할 수 있다. Figures 2a to 2c is a result of evaluating the BMD using the corrosion solution and Wright corrosion solution of the present invention for a sample of a silicon wafer normally subjected to a two-step heat treatment. As a result of the evaluation, the R-square is 98%, and it is possible to corrode the corrosion solution of the present invention to evaluate the BMD, thus replacing the conventional corrosion solution containing hexavalent chromium.

하기 실시예를 들어 본 발명을 더욱 자세히 설명할 것이나, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 보호범위가 하기 실시예로 한정되는 의도는 아니다. The present invention will be described in more detail with reference to the following examples, but the following examples are only intended to illustrate the present invention, and the protection scope of the present invention is not intended to be limited to the following examples.

실시예 1: 본 발명의 부식액을 이용한 OiSF 평가Example 1 OiSF Evaluation Using Corrosive Solution of the Invention

3가지 실리콘웨이퍼를 각각 OiSF 2 단계로 열처리하였다. OiSF를 관찰하기 위해 O2 분위기에서 1000℃, 3시간동안 열처리한 후에, 습식 분위기하에서 1150℃, 2시간 열처리하여 시료를 준비하였다.Three silicon wafers were each heat-treated in two stages of OiSF. In order to observe OiSF, a sample was prepared by heat treatment at 1000 ° C. for 3 hours in an O 2 atmosphere and then heat treatment at 1150 ° C. for 2 hours in a wet atmosphere.

49% HF 96.9ml, 70% HNO3 971.9 ml, 100% CH3COOH 639.2 ml, 및 H2O 292 ml로 혼합하여 본 발명에 따른 부식액을 제조하였다. 상온, 및 상압하에서, 상기 시료를 부식액 넣고, 교반을 하지 않고 4분간 처리한 후에, 광학 현미경 배율 200배로 OiSF 결함을 찾고 현미경의 Count 기능을 이용하여 결함의 밀도를 평가하였다. 상기 부식액으로 처리된 웨이퍼의 사진을 도 1a에 나타냈다, 또한 상기 3가지 시료에 대한 결정결함을 개수한 것을 도 1b에 나타내고, 이를 회귀분석한 결과를 도 1c에 나타냈다. A corrosive solution according to the invention was prepared by mixing with 49% HF 96.9 ml, 70% HNO 3 971.9 ml, 100% CH 3 COOH 639.2 ml, and H 2 O 292 ml. At room temperature and atmospheric pressure, the sample was placed in a corrosive solution and treated for 4 minutes without stirring. Then, the OiSF defect was found at an optical microscope magnification of 200 times, and the density of the defect was evaluated using the Count function of the microscope. The photograph of the wafer treated with the corrosive solution is shown in FIG. 1A, and the number of crystal defects for the three samples is shown in FIG. 1B, and the result of the regression analysis is shown in FIG. 1C.

비교예 1: Wright 부식액을 이용한 OiSF 평가Comparative Example 1: OiSF Evaluation Using Wright Corrosive

본 발명에 따른 실시예 1의 부식액 대신에 Wright 부식액을 상온 및 상압하에서 처리시간 5분으로 한 것을 제외하고는 상기 실시예 1과 실질적으로 동일한 방법으로 실험을 수행하였다. 상기 부식액으로 처리된 웨이퍼의 사진을 도 1a에 나타냈다. 또한 상기 3가지 시료에 대한 결정결함을 개수한 것을 도 1b에 나타내고, 이를 회귀분석한 결과를 도 1c에 나타냈다. The experiment was carried out in substantially the same manner as in Example 1, except that the Wright corrosion solution was treated for 5 minutes at room temperature and atmospheric pressure instead of the corrosion solution of Example 1 according to the present invention. The photograph of the wafer processed with the said corrosion liquid is shown to FIG. 1A. In addition, the number of crystal defects for the three samples is shown in Figure 1b, the results of the regression analysis is shown in Figure 1c.

도 1a, 1b, 1c는 실시예 1 및 비교예 1에 따라 OiSF 열처리된 시료에 대해 본 발명의 부식액과 Wright 부식액로 처리한 후 OiSF를 평가한 결과이다. 평가 결과 R-square가 90%로 본 발명의 부식액으로 OiSF를 평가하는 할 수 있을 뿐만 아니라 검출한 밀도까지도 기존의 Wright 처리한 것이라 거의 유사한 결과임을 회귀분석을 통해 확인할 수 있었다. 따라서 본 발명에 따른 부식액은 6가 크롬을 포함하고 있어 2006년도부터 사용이 규제되는 Wright 부식액을 대체할 수 있음을 알 수 있다. Figures 1a, 1b, 1c is the result of evaluating the OiSF after treatment with the corrosion solution and Wright corrosion solution of the present invention for OiSF heat-treated samples according to Example 1 and Comparative Example 1. As a result of the evaluation, the R-square was 90%, and it was possible to evaluate OiSF with the corrosion solution of the present invention, and the detected density was similar to that of the conventional Wright treatment, and it was confirmed through regression analysis. Therefore, it can be seen that the corrosion solution according to the present invention contains hexavalent chromium and thus can replace Wright corrosion solution, which is regulated from 2006.

실시예 2: 본 발명의 부식액을 이용한 BMD 평가Example 2 BMD Evaluation Using Corrosive Solution of the Invention

BMD(Bulk Micro Defect)를 관찰하기 위해, 4가지 실리콘 웨이퍼를 N2 분위기에서 800℃ 4시간 처리한 후에, 1000℃ 에서 16시간동안 열처리하였다. 상기 열처리된 웨이퍼를 다이아몬드 펜실(Diamond Pencile)로 절단하여 4가지 시료를 준비하였다.In order to observe the BMD (Bulk Micro Defect), four silicon wafers were treated at 800 ° C. for 4 hours in an N 2 atmosphere, and then heat-treated at 1000 ° C. for 16 hours. Four samples were prepared by cutting the heat-treated wafer with a diamond pencil.

상기 얻어진 시료에 대해, 49% HF 96.9ml, 70% HNO3 971.9 ml, 100% CH3COOH 639.2 ml, 및 H2O 292 ml로 혼합하여 본 발명에 따른 부식액을 제조하였다. 상온, 및 상압하에서, 상기 4가지 시료를 부식액 넣고, 교반을 하지 않고 4분간 처리한 후에, 광학 현미경 배율 200배로 BMD 결함을 찾고 현미경의 Count 기능을 이용하여 결함의 밀도를 평가하였다. 상기 부식액으로 처리된 웨이퍼의 사진을 도 2a에 나타냈다. 또한 상기 4가지 시료에 대한 결정결함을 개수한 것을 도 2b에 나타내고, 이를 회귀분석한 결과를 도 2c에 나타냈다. For the obtained sample, a corrosion solution according to the present invention was prepared by mixing with 96.9 ml 49% HF, 971.9 ml 70% HNO 3, 639.2 ml 100% CH 3 COOH, and 292 ml H 2 O. At room temperature and atmospheric pressure, the four samples were placed in a corrosion solution and treated for 4 minutes without stirring, and then BMD defects were found at an optical microscope magnification of 200 times, and the density of the defects was evaluated using the Count function of the microscope. The photograph of the wafer processed with the said corrosion liquid is shown to FIG. 2A. In addition, the number of crystal defects for the four samples is shown in Figure 2b, the results of the regression analysis is shown in Figure 2c.

비교예 2: Wright 부식액을 이용한 BMD 평가Comparative Example 2: BMD Evaluation with Wright Corrosive

본 발명에 따른 실시예 2의 부식액 대신에 Wright 부식액을 상온 및 상압하에서 처리시간 5분으로 한 것을 제외하고는 상기 실시예 1과 실질적으로 동일한 방법으로 실험을 수행하였다. 실험결과를 하기 도 2a 내지 도 2c에 나타냈다.The experiment was carried out in substantially the same manner as in Example 1, except that the Wright corrosion solution was treated for 5 minutes at room temperature and atmospheric pressure instead of the corrosion solution of Example 2 according to the present invention. Experimental results are shown in Figures 2a to 2c below.

도 2a 내지 도 2c는 실시예 2 및 비교예 2에 따라 정상 열처리된 시료에 대해 본 발명의 부식액과 Wright 부식액으로 처리한 후 BMD를 평가한 결과이다. 평가 결과 R-square가 98%로 본 발명의 부식액으로 BMD를 평가하는 할 수 있을 뿐만 아니라 검출한 밀도까지도 기존의 Wright 처리한 것이라 거의 유사한 결과임을 회귀분석을 통해 확인할 수 있었다. 따라서 본 발명에 따른 부식액은 6가 크롬을 포함하고 있어 2006년도부터 사용이 규제되는 Wright 부식액을 대체할 수 있음을 알 수 있다. Figures 2a to 2c is a result of evaluating the BMD after treatment with the corrosion solution and Wright corrosion solution of the present invention for a sample heat-treated according to Example 2 and Comparative Example 2. As a result of the evaluation, the R-square was 98%, and it was possible to evaluate the BMD with the corrosion solution of the present invention, and the detected density was confirmed by the regression analysis. Therefore, it can be seen that the corrosion solution according to the present invention contains hexavalent chromium and thus can replace Wright corrosion solution, which is regulated from 2006.

상기 실시예 및 비교예를 통해, 본 발명에 따른 부식액은 실리콘웨이퍼의 결정 결함, 바람직하게는 OiSF 및 BMD을 평가할 수 있고, 종래의 결정 결함 평가용 부식액과 비교할 경우 HF: HNO3, CH3COOH, H2O를 제외하고는 금속과 같은 첨가물이나 6가 크롬을 함유하지 않은 우수한 부식액이다. Through the above examples and comparative examples, the corrosion solution according to the present invention can evaluate crystal defects of silicon wafers, preferably OiSF and BMD, and when compared with conventional corrosion defects for crystal defect evaluation, HF: HNO 3, CH 3 COOH, H 2 O Except it is an excellent corrosion solution without additives such as metals or hexavalent chromium.

상기에서는 본 발명의 바람직한 실시 예에 대하여 설명하였지만, 본 발명은 이에 한정되는 것이 아니고 특허청구범위와 발명의 상세한 설명 및 첨부한 도면의 범위 안에서 여러 가지로 변형하여 실시하는 것이 가능하고 이 또한 본 발명의 범위에 속하는 것은 당연하다.Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the range of.

본 발명은 실리콘웨이퍼의 결정 결함 평가용 부식액을 제공하여, 2006년부터 규제 대상인 Cr을 함유하지 않고, 또한 종래 기술에서 사용한 Cu(NO3)2나 AgNO3 를 함유하지 않았으면서 빠르고 정확한 결정 결함을 평가를 할 수 있어 실리콘웨이퍼의 결정 결함 평가에 유용하게 사용될 수 있다. The present invention provides a corrosion solution for evaluating crystal defects of silicon wafers, and since 2006, it does not contain Cr, which is regulated, and does not contain Cu (NO 3 ) 2 or AgNO 3 , which is used in the prior art. The evaluation can be useful for the evaluation of crystal defects in silicon wafers.

Claims (6)

49% HF : 70% HNO3 : 100% CH3COOH : H2O = 0.5~1.5: 5 ~ 15 : 4~10 : 2~4 (부피비)로 포함하는,49% HF: 70% HNO 3 : 100% CH 3 COOH: H 2 O = 0.5 to 1.5: 5 to 15: 4 to 10: 2 to 4 (volume ratio), including 실리콘웨이퍼(silicon wafer)의 산화유기적층 결함(OiSF) 및 벌크미세결함(BMD)의 결정 결함 평가용 부식액.Corrosion solution for the evaluation of crystal defects of oxidized organic stacked defects (OiSF) and bulk fine defects (BMD) of silicon wafers. 삭제delete 제1항에 따른 실리콘웨이퍼의 결정결함 평가용 부식액으로 실리콘웨이퍼(silicon wafer)를 3분 내지 5분간 처리하고, 현미경을 사용하여 산화유기적층 결함(OiSF) 및 벌크미세결함(BMD)을 동시에 평가하는 것을 포함하는,A silicon wafer is treated for 3 to 5 minutes with a corrosion defect for evaluating crystal defects of the silicon wafer according to claim 1, and an oxide organic lamination defect (OiSF) and a bulk fine defect (BMD) are simultaneously evaluated using a microscope. Including doing it, 실리콘 웨이퍼의 산화유기적층 결함(OiSF) 및 벌크미세결함(BMD)의 결정 결함 평가방법.A method for evaluating crystal defects of oxidized organic stacked defects (OiSF) and bulk fine defects (BMD) of a silicon wafer. 삭제delete 제 3 항에 있어서, 상기 부식액의 처리는 상온 및 상압하에서 수행하는 것인 실리콘 웨이퍼의 결정 결함 평가방법. The method of evaluating crystal defects of a silicon wafer according to claim 3, wherein the treatment of the corrosion solution is performed at room temperature and atmospheric pressure. 제 3 항에 있어서, 상기 부식액의 처리는 교반하지 않고 수행하는 것을 특징 으로 하는 실리콘 웨이퍼의 결정 결함 평가방법. 4. The method of evaluating crystal defects of a silicon wafer according to claim 3, wherein the treatment of the corrosion solution is performed without stirring.
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