KR20000038448A - Method for fabricating ferroelectric thin film device using oxygen plasma - Google Patents
Method for fabricating ferroelectric thin film device using oxygen plasma Download PDFInfo
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- KR20000038448A KR20000038448A KR1019980053461A KR19980053461A KR20000038448A KR 20000038448 A KR20000038448 A KR 20000038448A KR 1019980053461 A KR1019980053461 A KR 1019980053461A KR 19980053461 A KR19980053461 A KR 19980053461A KR 20000038448 A KR20000038448 A KR 20000038448A
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Abstract
Description
본 발명은 강유전체를 이용한 반도체 소자의 제조에 관한 것으로, 특히 강유전체를 이용한 반도체 소자의 제조시 강유전체 박막표면에 존재하는 산소공핍(oxygen vacancy)이나 산소관련결함(oxygen-related defect)을 제거 또는 억제하여 강유전체 소자의 신뢰도를 상승시키고, 소자의 신뢰도를 높이는 공정에 소요되는 시간을 단축하기 위한 방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the fabrication of semiconductor devices using ferroelectrics. In particular, the manufacturing of semiconductor devices using ferroelectrics removes or suppresses oxygen vacancy or oxygen-related defects on the surface of a ferroelectric thin film. The present invention relates to a method for increasing the reliability of a ferroelectric device and reducing the time required for the process of increasing the reliability of the device.
일반적으로 DRAM(Dynamic Random Access Memory, 동적 임의 접근 기억 장치) 제조공정에서는 전하량을 저장하기 위한 커패시터가 필요한데 이 구조가 매우 복잡하다. DRAM의 집적도가 높을수록 커패시터는 더 복잡해져야 하는데, 현재 256MB 정도가 제조할 수 있는 한계로 여겨지고 있다. 따라서 1GB 이상의 DRAM 제조에는 초고집적도의 커패시터를 제작하든지, 아니면 다른 물질로 제작하여야 한다. 따라서 본 발명은 1GB 이상의 DRAM이나 64KB 이상의 FeRAM(Ferroelectric Random Access Memory)의 제조에 적용되며, gate oxide를 대체하는 물질로 응용가능하다.In general, a DRAM (Dynamic Random Access Memory) manufacturing process requires a capacitor to store the amount of charge, the structure is very complicated. The higher the density of DRAMs, the more complex the capacitors are, and currently around 256MB is considered a manufacturing limit. Therefore, the production of ultra-high-density capacitors, or other materials, must be made for DRAM production over 1GB. Therefore, the present invention is applied to the manufacture of DRAM of 1GB or more or FeRAM (Ferroelectric Random Access Memory) of 64KB or more, and is applicable to a material replacing gate oxide.
그리고 강유전체 박막표면에 존재하는 산소공핍이란 다음을 의미한다. 즉, 이상적인 PZT(Pb(Zr, Ti)O3, 지르콘·티탄산 납) 박막에는 산소원자가 격자내의 제 위치에 존재하지만 실제로는 산소가 격자에서부터 빠져나오게 되며, 이 때 산소 빈자리를 산소공핍이라 한다. 이러한 산소공핍은 박막성장공정이나 열처리 공정 등에서 발생할 수 있다. 또한 산소관련결함이란 산소 원자가 격자 내에서 만드는 결함으로 산소공핍 등을 말한다.Oxygen depletion on the ferroelectric thin film surface means the following. That is, in an ideal PZT (Pb (Zr, Ti) O 3 , lead zircon titanate) thin film, oxygen atoms are present in the lattice, but oxygen is actually released from the lattice, and oxygen vacancies are called oxygen depletion. Such oxygen depletion may occur in a thin film growth process or a heat treatment process. In addition, oxygen-related defects are defects that oxygen atoms make in the lattice, such as oxygen depletion.
도1a 및 도1b는 종래의 강유전체 박막소자 제조공정을 보인 단면도이다.1A and 1B are cross-sectional views illustrating a conventional ferroelectric thin film device manufacturing process.
도2a 내지 도2c는 본 발명의 실시예에 의한 산소플라즈마를 이용한 강유전체 박막소자의 제조공정을 보인 단면도이며,2A to 2C are cross-sectional views illustrating a manufacturing process of a ferroelectric thin film device using an oxygen plasma according to an embodiment of the present invention.
도3은 본 발명에 의한 산소플라즈마를 이용한 강유전체 박막소자와 종래 강유전체 박막소자의 사이클 함수를 보인 그래프이고,Figure 3 is a graph showing the cycle function of the ferroelectric thin film device and the conventional ferroelectric thin film device using the oxygen plasma according to the present invention,
도4는 본 발명에 의한 산소플라즈마를 이용한 강유전체 박막소자와 종래 강유전체 박막소자의 누설전류밀도를 보인 그래프이다.Figure 4 is a graph showing the leakage current density of the ferroelectric thin film device and the conventional ferroelectric thin film device using the oxygen plasma according to the present invention.
먼저, 도1a에 도시한 바와 같이, 하부전극(예를 들면, 백금(platinum, Pt) 전극)(1) 위에 강유전체(예를 들면, PZT) 박막(2)을 성장시킨다. 그러면 하부전극(1)과 강유전체 박막(2)의 경계면에서 접촉효과에 의한 산소공핍이나 산소관련결함(4)이 발생한다. 또한 하부전극(1)과의 경계면 이외의 면에서도 강유전체 박막은 산소공핍이나 산소관련결함(4)을 갖는다.First, as shown in FIG. 1A, a ferroelectric (for example, PZT) thin film 2 is grown on a lower electrode (for example, a platinum (Pt) electrode) 1. Then, oxygen depletion or oxygen-related defect 4 due to a contact effect occurs at the interface between the lower electrode 1 and the ferroelectric thin film 2. The ferroelectric thin film also has oxygen depletion or oxygen-related defects 4 at surfaces other than the interface with the lower electrode 1.
또한, 도1b에서, 강유전체 박막(2)을 산소가스 또는 질소가스 상태에 노출시켜 열처리를 수행하고, 강유전체 박막(2) 위에 상부전극(예를 들면, Pt)(3)을 성장시킨다. 이러한 열처리는 강유전체 소자의 초기적 특성을 높이기 위한 것으로, 이때의 열처리 온도는 300℃ 이상이고, 4시간 정도의 열처리 시간이 필요하다. 여기서 초기적 특성이란 강유전체 박막의 신뢰도를 테스트하기 위해 박막에 가해주는 전기적 스트레스의 일종인 피로테스트를 하기 전에 측정한 특성을 의미한다.In addition, in FIG. 1B, the ferroelectric thin film 2 is exposed to an oxygen gas or nitrogen gas state to perform heat treatment, and an upper electrode (for example, Pt) 3 is grown on the ferroelectric thin film 2. This heat treatment is to increase the initial characteristics of the ferroelectric element, the heat treatment temperature at this time is 300 ℃ or more, and needs about 4 hours of heat treatment time. Here, the initial characteristic means a characteristic measured before the fatigue test, which is a kind of electrical stress applied to the thin film to test the reliability of the ferroelectric thin film.
이에 따라 강유전체 박막(2)과 상부전극(3)의 경계면에 있던 산소관련결함(4)은 더욱 커지게 된다.As a result, the oxygen-related defect 4 at the interface between the ferroelectric thin film 2 and the upper electrode 3 becomes larger.
그리고 300℃ 이하의 저온에서 한 열처리는 많은 시간을 필요로 하는데, 열처리 시간을 줄이고 좋은 박막의 형상을 위해서는 300℃ 이상의 열처리 온도에서 4시간 이상의 처리가 필요하다.And the heat treatment at a low temperature of less than 300 ℃ requires a lot of time, in order to reduce the heat treatment time and the shape of a good thin film is required more than 4 hours at the heat treatment temperature of 300 ℃ or more.
그러나 종래의 강유전체 박막소자 제조방법은 산소관련결함이 커지게 되어 강유전체 소자의 수율과 신뢰도를 크게 떨어뜨리고, 소자의 신뢰도를 높이기 위한 300℃ 이상의 열처리에 걸리는 시간이 긴 단점이 있었다.However, the conventional ferroelectric thin film device manufacturing method has a disadvantage in that the oxygen-related defects increase, which greatly reduces the yield and reliability of the ferroelectric device, and takes a long time for heat treatment of 300 ° C. or more to increase the reliability of the device.
이에 본 발명은 상기와 같은 종래의 제반 문제점을 해소하기 위해 제안된 것으로, 본 발명의 목적은 강유전체를 이용한 반도체 소자의 제조시 강유전체 박막표면에 존재하는 산소공핍이나 산소관련결함을 제거 또는 억제하여 강유전체 소자의 신뢰성을 상승시키고, 소자의 신뢰도를 높이는 공정에 소요되는 시간을 단축할 수 있는 산소플라즈마를 이용한 강유전체 박막소자의 제조방법을 제공하는 데 있다.Accordingly, the present invention has been proposed to solve the above-mentioned conventional problems, and an object of the present invention is to eliminate or suppress oxygen depletion or oxygen-related defects existing on the surface of a ferroelectric thin film when manufacturing a semiconductor device using a ferroelectric. The present invention provides a method for manufacturing a ferroelectric thin film device using an oxygen plasma which can increase the reliability of the device and shorten the time required for the process of increasing the device reliability.
상기와 같은 목적을 달성하기 위하여 본 발명에 의한 산소플라즈마를 이용한 강유전체 박막소자의 제조방법은,Method of manufacturing a ferroelectric thin film device using an oxygen plasma according to the present invention in order to achieve the above object,
하부전극 위에 강유전체 박막을 성장시키고, 성장시킨 강유전체 박막 위에 산소 플라즈마 처리를 수행하여 강유전체 박막의 표면에 있는 산소관련결함을 감소시키며, 산소관련결함이 감소된 강유전체 박막 위에 상부전극을 증착시키는 것을 그 기술적 구성상의 특징으로 한다.The ferroelectric thin film is grown on the lower electrode, and oxygen plasma treatment is performed on the grown ferroelectric thin film to reduce oxygen-related defects on the surface of the ferroelectric thin film, and the upper electrode is deposited on the ferroelectric thin film with reduced oxygen-related defects. It is characterized by the configuration.
도1a 및 도1b는 종래의 강유전체 박막소자 제조공정을 보인 단면도이고,1A and 1B are cross-sectional views illustrating a conventional ferroelectric thin film device manufacturing process.
도2a 내지 도2c는 본 발명의 실시예에 의한 산소플라즈마를 이용한 강유전체 박막소자의 제조공정을 보인 단면도이며,2A to 2C are cross-sectional views illustrating a manufacturing process of a ferroelectric thin film device using an oxygen plasma according to an embodiment of the present invention.
도3은 본 발명에 의한 산소플라즈마를 이용한 강유전체 박막소자와 종래 강유전체 박막소자의 사이클 함수를 보인 그래프이고,Figure 3 is a graph showing the cycle function of the ferroelectric thin film device and the conventional ferroelectric thin film device using the oxygen plasma according to the present invention,
도4는 본 발명에 의한 산소플라즈마를 이용한 강유전체 박막소자와 종래 강유전체 박막소자의 누설전류밀도를 보인 그래프이다.Figure 4 is a graph showing the leakage current density of the ferroelectric thin film device and the conventional ferroelectric thin film device using the oxygen plasma according to the present invention.
＜도면의 주요 부분에 대한 부호의 설명＞<Description of the code | symbol about the principal part of drawing>
11 : 하부전극 12 : 강유전체 박막11 lower electrode 12 ferroelectric thin film
13 : 상부전극 14 : 산소관련결함13: upper electrode 14: oxygen-related defect
이하, 상기와 같은 본 발명 산소플라즈마를 이용한 강유전체 박막소자의 제조방법의 기술적 사상에 따른 일실시예를 첨부한 도면에 의거 상세히 설명하면 다음과 같다.Hereinafter, an embodiment according to the technical idea of the method of manufacturing a ferroelectric thin film device using the present invention oxygen plasma as described above in detail with reference to the accompanying drawings.
도2a 내지 도2c는 본 발명의 실시예에 의한 산소플라즈마를 이용한 강유전체 박막소자의 제조공정을 보인 단면도이다.2A to 2C are cross-sectional views illustrating a manufacturing process of a ferroelectric thin film device using an oxygen plasma according to an embodiment of the present invention.
먼저, 도2a에 도시한 바와 같이, 하부전극(11) 위에 강유전체 박막(12)을 증착시킨다. 이때 하부전극(11)은 Pt/Ti/SiO2/Si(100)(백금/티타늄/실리콘산화막/단결정실리콘) 기판을 사용할 수 있다. 그리고 강유전체 박막(12)은 PZT 박막을 사용하고, 졸-겔 방법(sol-gel process)으로 성장시킨다. 여기서 졸-겔 방법은 출발원료가 액체인 상태에서, 미립자를 포함한 졸(콜로이드)의 상태를 거쳐, 고체의 골격 틈 사이에 액체 등을 함유한 상태의 겔을 통과시켜 유리나 세라믹스 등의 무기재료를 만드는 방법이다.First, as shown in FIG. 2A, a ferroelectric thin film 12 is deposited on the lower electrode 11. In this case, the lower electrode 11 may use a Pt / Ti / SiO 2 / Si (100) (platinum / titanium / silicon oxide film / single crystal silicon) substrate. In addition, the ferroelectric thin film 12 uses a PZT thin film and is grown by a sol-gel process. Here, the sol-gel method passes through a sol (colloid) containing fine particles in a state where the starting material is a liquid and passes a gel containing a liquid or the like between the solid skeletal gaps to form an inorganic material such as glass or ceramics. How to make.
그러면 하부전극(11)과 강유전체 박막(12)의 경계면에서 접촉효과에 의한 산소공핍이나 산소관련결함(14)이 발생한다. 또한 하부전극(11)과의 경계면 이외의 면에서도 강유전체 박막(12)은 산소공핍이나 산소관련결함(14)을 갖는다.Then, oxygen depletion or oxygen-related defects 14 due to a contact effect occur at the interface between the lower electrode 11 and the ferroelectric thin film 12. The ferroelectric thin film 12 also has oxygen depletion or oxygen-related defects 14 at surfaces other than the interface with the lower electrode 11.
그리고, 도2b에서, RF(Radio Frequency, 무선)를 이용하여 중성기체를 플라즈마 상태로 만드는 반응기인 RF 플라즈마 발생기에서 산소 플라즈마를 상온 내지 700℃의 온도영역 내에서 60W - 0.7Torr의 처리조건으로 일정 시간 동안 처리하여, 산소플라즈마 처리를 수행한다. 그러면 강유전체 박막(12)의 표면에 있는 산소공핍이나 산소관련결함(14)은 감소하게 된다.In FIG. 2B, in the RF plasma generator, which is a reactor for making a neutral gas into a plasma state using RF (Radio Frequency, radio), oxygen plasma is constant at a processing condition of 60W-0.7Torr in a temperature range of room temperature to 700 ° C. By treatment for a time, oxygen plasma treatment is performed. This reduces oxygen depletion or oxygen-related defects 14 on the surface of the ferroelectric thin film 12.
또한, 도2c에서, 산소플라즈마 처리를 수행한 이후에 직류전원을 사용하여 물질을 증착시키는 DC(Direct Current) 스푸터링(sputtering) 방법으로 상부전극(13)인 백금전극을 증착시킨다.In addition, in FIG. 2C, the platinum electrode, which is the upper electrode 13, is deposited by a direct current sputtering method in which a material is deposited using a direct current power source after performing an oxygen plasma treatment.
여기서 다음의 표1은 도2b에서 산소플라즈마 처리공정을 하지 않을 경우, 30분, 60분, 90분, 120분간 산소플라즈마 처리공정을 수행한 경우의 결과표이다.Here, Table 1 is a result table when the oxygen plasma treatment process is performed for 30 minutes, 60 minutes, 90 minutes, and 120 minutes when the oxygen plasma treatment process is not performed in FIG. 2B.
이러한 표1은 ±10V와
이에 따라 산소플라즈마 처리를 하지 않은 시편은 피로 전과 비교한 분율이 59%인데 반해, 본 발명에 의해 30분 내지 120분간 산소플라즈마 처리를 시편은 75% 내지 83%의 높은 잔여분극을 보여준다.Accordingly, while the specimen without oxygen plasma treatment had a 59% fraction as compared to before fatigue, the specimen exhibited a high residual polarization of 75% to 83% with oxygen plasma treatment for 30 to 120 minutes according to the present invention.
도3은 본 발명에 의한 산소플라즈마를 이용한 강유전체 박막소자와 종래 강유전체 박막소자의 사이클 함수를 보인 그래프로써, 표1의 결과를 그래프로 보인 것이다.3 is a graph showing a cycle function of a ferroelectric thin film device using an oxygen plasma and a conventional ferroelectric thin film device according to the present invention, and the results of Table 1 are shown graphically.
이처럼 피로 테스트 후에도 잔여분극인 2Pr 값이 많이 남는 것이 우수한 소자이고, 이는 피로 전과 비교한 분율이 높을수록 신뢰도 있는 소자라는 것을 의미한다. 표1과 도3에서 보면, 산소플라즈마 처리를 하지 않은 시편이 가장 적은 2Pr 값을 보여 산소플라즈마 처리가 피로를 효과적으로 억제할 수 있어 소자의 신뢰도를 높일 수 있음을 알 수 있다.As such, the residual polarization value of 2Pr remains even after the fatigue test, and this means that the higher the fraction compared to before fatigue, the more reliable the device is. As shown in Table 1 and Figure 3, the specimen without oxygen plasma treatment shows the smallest 2Pr value, it can be seen that the oxygen plasma treatment can effectively suppress the fatigue, thereby improving the reliability of the device.
다음의 표2는 Pt/PZT/Pt 소자에 피로를 108가한 후에 측정한 누설전류 밀도이다.The following Table 2 shows the leakage current density measured after the blood to the Pt / PZT / Pt elements 10 8 were added.
그리고 도4는 본 발명에 의한 산소플라즈마를 이용한 강유전체 박막소자와 종래 강유전체 박막소자의 누설전류밀도를 보인 그래프로써, 표2의 결과를 그래프로 보인 것이다.4 is a graph showing the leakage current density of the ferroelectric thin film device and the conventional ferroelectric thin film device using the oxygen plasma according to the present invention, the results of Table 2 are shown as a graph.
표2와 도4에서와 같이, 종래의 산소플라즈마 처리를 하지 않은 시편은 누설전류밀도가 높은 반면에 30분 내지 120분간 산소플라즈마 처리를 한 시편은 누설전류밀도가 매우 낮아 피로 후에도 소자의 신뢰도가 매우 높음을 알 수 있다.As shown in Tables 2 and 4, the specimens without conventional oxygen plasma treatment have a high leakage current density, whereas the specimens subjected to oxygen plasma treatment for 30 to 120 minutes have a very low leakage current density, so that the reliability of the device is maintained even after fatigue. It is very high.
이처럼 본 발명은 강유전체 박막표면에 존재하는 산소관련결함을 제거 또는 억제하여 강유전체 소자의 신뢰도를 상승시키게 되는 것이다.As such, the present invention removes or suppresses oxygen-related defects existing on the surface of the ferroelectric thin film, thereby increasing the reliability of the ferroelectric element.
이상에서 본 발명의 바람직한 실시예를 설명하였으나, 본 발명은 다양한 변화와 변경 및 균등물을 사용할 수 있다. 본 발명은 상기 실시예를 적절히 변형하여 동일하게 응용할 수 있음이 명확하다. 즉, 초기적 특성 뿐만 아니라 피로 후에도 우수한 제품특성을 보여 신뢰도 있는 반도체 소자제품에 적용할 수 있다. 따라서 상기 기재 내용은 하기 특허청구범위의 한계에 의해 정해지는 본 발명의 범위를 한정하는 것이 아니다.Although the preferred embodiment of the present invention has been described above, the present invention may use various changes, modifications, and equivalents. It is clear that the present invention can be applied in the same manner by appropriately modifying the above embodiments. That is, it can be applied to reliable semiconductor device products because it shows excellent product characteristics even after fatigue as well as initial characteristics. Accordingly, the above description does not limit the scope of the invention as defined by the limitations of the following claims.
이상에서 살펴본 바와 같이, 본 발명에 의한 산소플라즈마를 이용한 강유전체 박막소자의 제조방법은 종래의 열처리 방법에 의해 비해 공정시간이 짧고, 초기적 특성 뿐만 아니라 피로 후에도 우수한 제품특성을 보여 신뢰도 있는 반도체 소자를 제조할 수 있는 효과가 있게 된다.As described above, the method of manufacturing the ferroelectric thin film device using the oxygen plasma according to the present invention has a shorter processing time than the conventional heat treatment method, and shows a reliable semiconductor device after initial fatigue as well as excellent product characteristics after fatigue. There is an effect that can be produced.
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