KR19980084299A - Method for producing oxide etching solution with cleaning ability - Google Patents
Method for producing oxide etching solution with cleaning ability Download PDFInfo
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- KR19980084299A KR19980084299A KR1019970020052A KR19970020052A KR19980084299A KR 19980084299 A KR19980084299 A KR 19980084299A KR 1019970020052 A KR1019970020052 A KR 1019970020052A KR 19970020052 A KR19970020052 A KR 19970020052A KR 19980084299 A KR19980084299 A KR 19980084299A
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Abstract
본 발명은 반도체 소자 제조방법에 관한 것으로, 특히 식각과 세정 공정을 동시에 행할 수 있는 세정 능력을 갖는 산화막 식각용액 제조방법에 관한 것이다. 수산화암모늄(NH4OH)과 과산화수소(H2O2)와 탈이온수가 소정 비로 혼합되어 있는 제1 용액(SC-1)에 수산화암모늄의 혼합비를 두배로 늘림과 동시에 증가된 수산화암모늄의 몰(mol)수만큼 불화수소(HF)를 추가한다. 항온 조건에서 상기 수산화암모늄과 불화수소가 추가된 제1 용액의 반응종결점을 찾아 평형상태 도달하도록 함으로써 수산화암모늄(NH4OH)과 과산화수소(H2O2)와 불화암모늄(NH4F)과 불화수소(HF)와 탈이온수가 소정 비로 혼합되어 있는 제2 용액을 만든다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a semiconductor device, and more particularly, to a method of manufacturing an oxide film etching solution having a cleaning ability capable of simultaneously performing an etching process and a cleaning process. The molar amount of ammonium hydroxide increased at the same time by doubling the mixing ratio of ammonium hydroxide to the first solution (SC-1) in which ammonium hydroxide (NH 4 OH), hydrogen peroxide (H 2 O 2 ) and deionized water were mixed in a predetermined ratio ( Add hydrogen fluoride (HF) by the number of moles. Under constant temperature conditions, ammonium hydroxide (NH 4 OH), hydrogen peroxide (H 2 O 2 ), ammonium fluoride (NH 4 F) and ammonium hydroxide and hydrogen fluoride (NH 4 F) A second solution is prepared in which hydrogen fluoride (HF) and deionized water are mixed in a predetermined ratio.
Description
본 발명은 반도체 소자 제조방법에 관한 것으로, 특히 식각과 세정 공정을 동시에 행할 수 있는 세정 능력을 갖는 산화막 식각용액 제조방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a semiconductor device, and more particularly, to a method of manufacturing an oxide film etching solution having a cleaning ability capable of simultaneously performing an etching process and a cleaning process.
불화암모늄(NH4F)과 불화수소(HF)와 탈이온수(DIW)를 소정비로 혼합한 용액을 이용하여 각종 산화막을 식각(또는 스트립(strip))하는 것은 반도체 공정에 있어서 보편화되어 있다. 그러나, 용액 자체의 파티클 및 식각(또는 스트립) 시 발생하는 부산물에 의한 웨이퍼의 오염 때문에 후속 세정 공정이 필수적이다.Etching (or stripping) various oxide films using a solution in which ammonium fluoride (NH 4 F), hydrogen fluoride (HF) and deionized water (DIW) are mixed at a predetermined ratio is common in a semiconductor process. However, subsequent cleaning processes are essential because of contamination of the wafer by the by-products generated during the etching and / or stripping of the solution itself.
예를 들어, SBOE (NH4F, HF 및 탈이온수가 소정비로 혼합되어 있는 식각용액)로 화학 기상 증착(CVD) 방식으로 증착된 산화막질인 BPSG (Boro-Phosphorus Silicate Glass)막을 식각했다면, 이후 공정 진행을 위해서는 SC-1(NH4OH, H2O2및 탈이온수가 소정비로 혼합되어 있는 세정용액) 용액을 이용하여 웨이퍼를 세정해야 한다. SC-1 (1:1:5, NH4OH(29 w/w%): H2O2(30%, not stablized): DIW, v/v/v)용액을 사용한 세정 공정은 유기물 및 잔유 금속(trace metal)을 제거하기 위한 세정 공정으로서, 현재 습식 세정에 있어서는 가장 일반화되어 있다.For example, after etching a BPSG (Boro-Phosphorus Silicate Glass) film deposited by chemical vapor deposition (CVD) with SBOE (an etching solution containing NH 4 F, HF and deionized water in a predetermined ratio), In order to proceed with the process, the wafer should be cleaned using a solution of SC-1 (NH 4 OH, H 2 O 2 and deionized water in a predetermined ratio). SC-1 (1: 1: 5, NH 4 OH (29 w / w%): H 2 O 2 (30%, not stablized): DIW, v / v / v) As a cleaning process for removing trace metal, it is currently most common in wet cleaning.
상기한 바와 같은 SBOE 용액을 이용한 산화막의 식각은 용액 자체의 파티클 및 식각 시 발생하는 부산물에 의한 웨이퍼의 오염을 유발하기 때문에 세정공정이 후속으로 수반되어야 하나, 후속으로 진행되는 세정 공정에서 주로 사용되는 SC-1 용액은 산화막을 식각하는 자체 특성을 갖고 있으며, CVD막의 경우 상당한 식각량을 보이는 경우도 있다.Since the etching of the oxide film using the SBOE solution as described above causes contamination of the wafer by the particles and by-products generated during the etching, the cleaning process must be subsequently accompanied, but is mainly used in the subsequent cleaning process. The SC-1 solution has its own characteristic of etching an oxide film, and in the case of a CVD film, a considerable amount of etching may be shown.
또한, 불화암모늄과 불화수소 및 탈이온수를 혼합한 용액을 이용한 산화막 식각공정은 최소한 두 단계(식각 단계와 세정 단계)로 구성되어야 하므로 공정 시간 및 설비 측면에서 많은 손실이 발생한다.In addition, since the oxide film etching process using a mixture of ammonium fluoride, hydrogen fluoride and deionized water should be composed of at least two steps (etching step and washing step), a lot of loss occurs in terms of process time and equipment.
본 발명의 목적은 산화막을 식각하는 단계와 세정하는 단계를 하나의 단계로 행할 수 있는 세정 능력을 갖는 산화막 식각 용액 제조방법을 제공하는데 있다.SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing an oxide film etching solution having a cleaning ability capable of etching and cleaning an oxide film in one step.
상기 목적을 달성하기 위한, 본 발명에 의한 세정 능력을 갖는 산화막 식각용액 제조방법은, 수산화암모늄(NH4OH)과 과산화수소(H2O2)와 탈이온수가 소정 비로 혼합되어 있는 제1 용액(SC-1)에 암모니아의 혼합비를 두배로 늘림과 동시에 증가된 수산화암모늄의 몰(mol)수만큼 불화수소(HF)를 추가하는 공정; 및 항온 조건에서 상기 수산화암모늄과 불화수소가 추가된 제1 용액의 반응종결점을 찾아 평형상태 도달하도록 함으로써 수산화암모늄(NH4OH)과 과산화수소(H2O2)와 불화암모늄(NH4F)과 불화수소(HF)와 탈이온수가 소정 비로 혼합되어 있는 제2 용액을 만드는 공정을 포함하는 것을 특징으로 한다.In order to achieve the above object, the method for producing an oxide film etching solution having a cleaning ability according to the present invention includes a first solution in which ammonium hydroxide (NH 4 OH), hydrogen peroxide (H 2 O 2 ), and deionized water are mixed in a predetermined ratio ( Doubling the mixing ratio of ammonia to SC-1) and adding hydrogen fluoride (HF) by the number of moles of ammonium hydroxide increased; And ammonium hydroxide (NH 4 OH), hydrogen peroxide (H 2 O 2 ), and ammonium fluoride (NH 4 F) by finding an end point of reaction of the first solution to which ammonium hydroxide and hydrogen fluoride are added at constant temperature. And a second solution in which hydrogen fluoride (HF) and deionized water are mixed in a predetermined ratio.
이하, 본 발명에 의한 세정 능력을 갖는 산화막 식각용액 제조방법에 대해 더욱 자세하게 설명하고자 한다.Hereinafter, a method of preparing an oxide film etching solution having a cleaning ability according to the present invention will be described in more detail.
본 발명은 SBOE의 산화막 식각 능력과 SC-1의 세정 능력을 조합한 용액을 제조한 후, 이를 통해 산화막 식각 단계와 세정 단계를 동시에 진행할 수 있도록 한 것이다.The present invention is to prepare a solution that combines the oxide etching ability of the SBOE and the cleaning ability of SC-1, through which the oxide etching step and the cleaning step can be performed at the same time.
SC-1(1:1:5, NH4OH(29 w/w%): H2O2(30%, not stablized): DIW, v/v/v)용액에서 수산화암모늄(NH4OH)의 비율을 두배(1→2)로 증가시킨 후, 여기에 증가한 수산화암모늄의 몰(mol)수 만큼의 불화수소(HF)를 추가한다. 이때, 추가된 불화수소(HF)는 수산화암모늄(NH4OH)과 반응하여 불화암모늄(NH4F)과 수증기(H2O)로 된다. 그러나, 온도 조절(25 - 80℃)을 통해 NH4OH + HF ↔ NH4F + H2O 반응의 평형 상수 및 반응 속도를 조절하면 (즉, 항온을 유지하되 온도의 변화를 관찰하여 반응종결점을 찾고 평형 상태에 도달하도록 하면) 완전한 정반응은 이루어지지 않으며, 혼합 용액은 수산화암모늄(NH4OH)과 과산화수소(H2O2)와 불화수소(HF)와 불화암모늄(NH4F)과 탈이온수(DIW)의 구성을 이루게된다.SC-1 (1: 1: 5, NH 4 OH (29 w / w%): H 2 O 2 (30%, not stablized): DIW, v / v / v) ammonium hydroxide (NH 4 OH) in solution After doubling the ratio of (1 → 2), add hydrogen fluoride (HF) as much as the number of moles of ammonium hydroxide increased. At this time, the added hydrogen fluoride (HF) reacts with ammonium hydroxide (NH 4 OH) to form ammonium fluoride (NH 4 F) and water vapor (H 2 O). However, by adjusting the equilibrium constant and reaction rate of NH 4 OH + HF ↔ NH 4 F + H 2 O reaction through temperature control (25-80 ℃) (that is, maintain the constant temperature, observe the change in temperature and terminate the reaction. When the point is found and equilibrium is reached, no complete reaction occurs, and the mixed solution contains ammonium hydroxide (NH 4 OH), hydrogen peroxide (H 2 O 2 ), hydrogen fluoride (HF), ammonium fluoride (NH 4 F) and It is made up of DI water.
즉, SC-1 용액에서 암모니아 비율을 두배로 증가시키고, 여기에 증가된 수산화암모늄의 몰수 만큼의 불화수소를 추가하였을 때 용액 내에서 일어나는 반응은 아래와 같다.That is, when the ammonia ratio is doubled in the SC-1 solution, and the hydrogen fluoride is added as much as the number of moles of ammonium hydroxide increased, the reaction occurring in the solution is as follows.
NH4OH + HF → NH4F + H2O --- (1)NH 4 OH + HF → NH 4 F + H 2 O --- (1)
(1)의 반응식에서 온도 조절(25 - 80℃)을 통해 각 분자의 해리상수 및 반응의 평형 상수 또는 반응 속도를 변화시키면, 반응은 정방향으로 완전히 진행되지 않으며 일정한 상태에서 평형을 유지하게 된다. 다시 말해, 수산화암모늄(NH4OH)과 과산화수소(H2O2)와 불화수소(HF)와 불화암모늄(NH4F)과 탈이온수(DIW)로 구성되는 혼합 용액이 되고, 항온 조건에서 일정한 비율을 갖게 된다.When the dissociation constant and the equilibrium constant or reaction rate of each molecule are changed through temperature control (25-80 ° C.) in the reaction of (1), the reaction does not proceed completely in the forward direction and remains in a constant state. In other words, a mixed solution consisting of ammonium hydroxide (NH 4 OH), hydrogen peroxide (H 2 O 2 ), hydrogen fluoride (HF), ammonium fluoride (NH 4 F), and deionized water (DIW), You have a ratio.
이와 같이 구성된 혼합용액에서 불화암모늄(NH4F)과 불화수소(HF)는 산화막을 식각하는 역할을 하며, 수산화암모늄(NH4OH)과 과산화수소(H2O2)는 산화막을 세정하는 역할을 하므로, 하나의 용액으로 식각 공정과 세정 공정을 동시에 행할 수 있다.In this mixed solution, ammonium fluoride (NH 4 F) and hydrogen fluoride (HF) serve to etch the oxide film, and ammonium hydroxide (NH 4 OH) and hydrogen peroxide (H 2 O 2 ) serve to clean the oxide film. Therefore, an etching process and a washing process can be performed simultaneously with one solution.
이때, 상술한 바와 같은 조합 공정이 진행되는 설비(bath)는 테플론(teflon) 재질로서 순환(circulation)을 통한 항온이 가능해야 하며, 부속 장비로서 수산화암모늄, 과산화수소, 불화수소 및 탈이온수를 정량 공급할 수 있는 장치가 필요하다. 또한, 조합 공정에 사용되는 화학용액으로는 반도체 등급(grade) (ex, NH4OH:MB-64, HF:SA-X, H2O2:MB-16H)으로서 불순물의 생성 및 촉매 역할을 최대한 억제할 수 있어야 한다.At this time, the bath (bath) where the combination process proceeds as described above should be capable of constant temperature through circulation as a teflon material, and supply ammonium hydroxide, hydrogen peroxide, hydrogen fluoride and deionized water as accessory equipment. You need a device that can. In addition, the chemical solution used in the combinatorial process is a semiconductor grade (ex, NH 4 OH: MB-64, HF: SA-X, H 2 O 2 : MB-16H), which plays an important role in generating impurities and acting as a catalyst. It should be as restrainable as possible.
본 발명에 의한 세정 능력을 갖는 산화막 식각용액 제조방법에 의하면, 산화막을 식각하는 단계과 세정하는 단계를 동시에 진행할 수 있는 용액을 제조할 수 있기 때문에, 첫째, 공정 시간을 단축시킬 수 있고, 둘째, 설비 측면에서는 소요되는 장치가 줄어들어 공정 단가를 줄일 수 있고, 셋째, 불화암모늄 등의 화학용액의 소비를 감소시킬 수 있으며, 넷째, 공정의 단순화로 설비성 사고 가능성을 줄일 수 있다.According to the method for producing an oxide film etching solution having a cleaning ability according to the present invention, since a solution capable of simultaneously etching and cleaning the oxide film can be prepared, firstly, the process time can be shortened, and secondly, the equipment can be prepared. In the aspect, the required equipment can be reduced to reduce the cost of the process, and third, the consumption of chemical solution such as ammonium fluoride can be reduced, and fourth, the possibility of equipment accidents can be reduced by the simplification of the process.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100319186B1 (en) * | 1999-03-26 | 2001-12-29 | 윤종용 | Method for fabricating a trench isolation |
| KR100338764B1 (en) * | 1999-09-20 | 2002-05-30 | 윤종용 | Cleaning solution for removing contaminants from surface of semiconductor substrate and cleaning method using thereof |
| KR100439103B1 (en) * | 2002-07-16 | 2004-07-05 | 주식회사 하이닉스반도체 | Manufacturing Method of Semiconductor Device |
| KR100775688B1 (en) * | 2004-02-16 | 2007-11-09 | 마쯔시다덴기산교 가부시키가이샤 | Method for manufacturing the semiconductor device |
| KR100827684B1 (en) * | 2001-10-30 | 2008-05-07 | 에이펫(주) | cleaning solution for semiconductor device and for semiconductor device-cleaning method using the same |
| US7579284B2 (en) | 2005-07-12 | 2009-08-25 | Samsung Electronics Co., Ltd | Etching solution, method of forming a pattern using the same, method of manufacturing a multiple gate oxide layer using the same and method of manufacturing a flash memory device using the same |
-
1997
- 1997-05-22 KR KR1019970020052A patent/KR19980084299A/en not_active Application Discontinuation
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100319186B1 (en) * | 1999-03-26 | 2001-12-29 | 윤종용 | Method for fabricating a trench isolation |
| KR100338764B1 (en) * | 1999-09-20 | 2002-05-30 | 윤종용 | Cleaning solution for removing contaminants from surface of semiconductor substrate and cleaning method using thereof |
| KR100827684B1 (en) * | 2001-10-30 | 2008-05-07 | 에이펫(주) | cleaning solution for semiconductor device and for semiconductor device-cleaning method using the same |
| KR100439103B1 (en) * | 2002-07-16 | 2004-07-05 | 주식회사 하이닉스반도체 | Manufacturing Method of Semiconductor Device |
| KR100775688B1 (en) * | 2004-02-16 | 2007-11-09 | 마쯔시다덴기산교 가부시키가이샤 | Method for manufacturing the semiconductor device |
| US7425745B2 (en) | 2004-02-16 | 2008-09-16 | Matsushita Electric Industrial Co., Ltd. | Semiconductor device and method for manufacturing the same |
| US7579284B2 (en) | 2005-07-12 | 2009-08-25 | Samsung Electronics Co., Ltd | Etching solution, method of forming a pattern using the same, method of manufacturing a multiple gate oxide layer using the same and method of manufacturing a flash memory device using the same |
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