KR100294850B1 - Manufacturing Method of PZT Thick Film Using Partially Melted Material - Google Patents
Manufacturing Method of PZT Thick Film Using Partially Melted Material Download PDFInfo
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- KR100294850B1 KR100294850B1 KR1019980022134A KR19980022134A KR100294850B1 KR 100294850 B1 KR100294850 B1 KR 100294850B1 KR 1019980022134 A KR1019980022134 A KR 1019980022134A KR 19980022134 A KR19980022134 A KR 19980022134A KR 100294850 B1 KR100294850 B1 KR 100294850B1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/093—Forming inorganic materials
- H10N30/097—Forming inorganic materials by sintering
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8548—Lead based oxides
- H10N30/8554—Lead zirconium titanate based
Abstract
본 발명은 부분용융물질을 이용하여 저온에서 PZT 후막을 제조하는 방법에 관한 것이다. PZT는 Pb1+x(ZryTi1-x)O3의 조성식을 가지며 전기적으로 우수한 압전 및 유전특성을 갖는 물질로써 PZT는 엑추에이터, 트랜스듀서, 캐퍼시터, 센서 등의 소자로 널리 이용되고 있다. PZT 후막 제조에 있어서는 소결온도가 1,000℃ 이상이면 소결시 및 집적시 실리콘 등의 반도체와 상호 확산반응이나 납성분의 휘발이 일어나 제조에 어려움이 있고, 소결조제를 첨가하여 소결온도를 낮추면 불순물 영향으로 PZT 특성이 저하되는 문제점이 있다. 본 발명은 PZT를 구성하는 원료물질 중에서 용융점이 낮은 물질(PbO, CH3COOPbㆍ3H2O, Pb(NO3)2등)과 용융점이 높은 물질(ZrO2, TiO2, PbZrO3, PbTiO3등)을 함께 사용하여 1,000℃ 이하의 온도에서 열처리하므로 PZT가 균일하고 미세한 입자들로 형성되며, 소결밀도가 높고 불순물이 함유되지 않아 압전 및 유전 특성이 우수할 뿐만 아니라 반응시간이 짧기 때문에 경제적으로 PZT를 제조할 수 있다.The present invention relates to a method for producing a PZT thick film at low temperature using a partially melted material. PZT has a composition formula of Pb 1 + x (Zr y Ti 1-x ) O 3 and has excellent electrical piezoelectric and dielectric properties, and PZT is widely used as an element for actuators, transducers, capacitors, and sensors. In the production of PZT thick film, when the sintering temperature is 1,000 ℃ or higher, it is difficult to manufacture due to mutual diffusion reaction and volatilization of lead component with semiconductors such as silicon during sintering and integration. There is a problem that PZT characteristics are degraded. In the present invention, materials having a low melting point (PbO, CH 3 COOPb • 3H 2 O, Pb (NO 3 ) 2, etc.) and materials having a high melting point (ZrO 2 , TiO 2 , PbZrO 3 , PbTiO 3) Etc.) together with heat treatment at a temperature below 1,000 ℃, PZT is formed into uniform and fine particles, and because it has high sintered density and no impurities, it has excellent piezoelectric and dielectric properties as well as short reaction time. PZT can be prepared.
Description
본 발명은 부분용융물질을 이용하여 저온에서 PZT 후막을 제조하는 방법에 관한 것이다. PZT는 Pb1+x(ZryTi1-x)O3의 조성식을 가지며 전기적으로 우수한 압전 및 유전특성을 갖는 물질로 널리 알려져 있다. 이러한 우수한 특성을 갖는 PZT는 엑추에이터, 트랜스듀서, 캐퍼시터, 센서 등의 소자로 널리 이용되는데, 최근 마이크로머시닝 기술의 급속한 발달과 함께 박막 또는 후막 형태 소자의 요구가 더욱 커지고 있는 추세이다. 특히 잉크젯프린터 헤드 등에서는 압전막의 변위와 힘이 크게 요구되고 장시간 사용을 위하여 열화특성이 우수한 마이크로 엑추에이터 재료로 PZT 후막이 요구되고 있다. 또한 실리콘웨이퍼 등과 같은 반도체 위에 집적시켜 PZT 후막을 제조할 경우 마이크로 디바이스를 제조하는데 있어 유리한 점이 매우 많다. 이러한 유사한 용도로 사용하기 위한 PZT 후막을 제조하는 종래의 기술은 PZT 원료분말에 유기물질을 혼합한 스크린 프린팅용 잉크를 원료로 사용하는 방법과 소결온도를 낮추기 위한 소결조제(Bi2O3, B2O3, CdO, PbO, PbF2, SiO2, V2O5, Nb2O5등)를 첨가한 원료를 사용하거나, 미세하게 분쇄한 원료분말을 사용하는 등의 방법들이 주류를 이루고 있다.The present invention relates to a method for producing a PZT thick film at low temperature using a partially melted material. PZT has a compositional formula of Pb 1 + x (Zr y Ti 1-x ) O 3 and is widely known as a material having excellent piezoelectric and dielectric properties. PZT having such excellent characteristics is widely used as an actuator, a transducer, a capacitor, a sensor, and the like. Recently, with the rapid development of micromachining technology, the demand for thin film or thick film type devices is increasing. In particular, inkjet printer heads and the like require a large displacement and force of the piezoelectric film, and a PZT thick film is required as a micro actuator material having excellent deterioration characteristics for long time use. In addition, when manufacturing a PZT thick film by integrating it on a semiconductor such as a silicon wafer, there are many advantages in manufacturing a micro device. Conventional techniques for producing PZT thick films for use in such similar applications include the use of screen printing inks mixed with organic materials in PZT raw powders as raw materials and sintering aids to lower the sintering temperature (Bi 2 O 3 , B Methods such as using raw materials added with 2 O 3 , CdO, PbO, PbF 2 , SiO 2 , V 2 O 5 , Nb 2 O 5, etc., or using finely ground raw powder .
그러나 이러한 종래의 기술을 사용하여 PZT 후막을 제조하는 경우 소결온도가 매우 높아 1,000℃ 이상의 온도에서는 소결시 및 집적시 실리콘 등의 반도체와 상호 확산반응이나 납성분의 휘발이 일어나 제조하기 매우 어렵고, 위에 열거한 소결조제를 첨가하면 소결온도를 1,000℃ 이하로 낮추는 것은 가능하나 첨가한 소결조제들의 영향으로 PZT 특성이 저하되는 문제점이 있다.However, when the PZT thick film is manufactured using such a conventional technique, the sintering temperature is very high, and at a temperature of 1,000 ° C. or more, it is difficult to manufacture the product due to the interdiffusion reaction or volatilization of lead components with semiconductors such as silicon during sintering and integration. If the listed sintering aids are added, it is possible to lower the sintering temperature to 1,000 ° C. or lower, but there is a problem in that PZT characteristics are degraded due to the effects of the added sintering aids.
본 발명은 종래 기술의 문제점을 해결하기 위한 것으로, PZT를 구성하는 원료물질로서 용융점이 낮은 산화납(PbO), 초산납(CH3COOPbㆍ3H2O), 질산납(Pb(NO3)2)등과 용융점이 높은 산화지르코늄(ZrO2), 산화티타늄(TiO2), 산화티타늄납(PbTiO3), 산화지르코늄납(PbZrO3)등을 함께 사용하여 낮은 온도의 열처리로 PZT를 형성시키는 방법으로서 PZT가 충분한 소결밀도를 갖고, Pb와 Si 등의 상호확산을 억제할 수 있으며, 반응에 필요한 시간이 짧아 경제적이고 소결후 균일하고 미세한 입자들로 형성되므로 우수한 압전 및 유전특성을 갖는 PZT 후막의 제조공정을 제공하고자 한다.The present invention is to solve the problems of the prior art, as a raw material constituting PZT, lead oxide (PbO), lead acetate (CH 3 COOPb · 3H 2 O), lead nitrate (Pb (NO 3 ) 2 ) having a low melting point PZT is formed by low temperature heat treatment using ZrO 2 (ZrO 2 ), titanium oxide (TiO 2 ), titanium oxide (PbTiO 3 ), lead zirconium oxide (PbZrO 3 ), etc. Has a sufficient sintering density, can suppress the interdiffusion of Pb and Si, and it is economical due to the short time required for the reaction and is formed into uniform and fine particles after sintering. To provide.
도 1 은 부분용융을 이용한 PZT 후막의 제조공정도.1 is a manufacturing process of the PZT thick film using partial melting.
도 2 는 본 발명으로 제조한 PZT 후막의 XRD 그래프2 is an XRD graph of a PZT thick film prepared according to the present invention.
도 3(a)는 본 발명의 원료분말을 이용하여 750℃에서 제조한 PZT 후막의 단면 및 표면을 기울인 SEM 사진Figure 3 (a) is a SEM photograph of the inclined cross section and surface of the PZT thick film prepared at 750 ℃ using the raw material powder of the present invention
(b)는 (a)를 40,000배의 고배율로 관찰한 SEM 사진이다.(b) is SEM image which observed (a) at high magnification of 40,000 times.
본 발명은 PZT형성을 위한 출발물질로서 낮은 융점을 갖는 산화납(PbO), 초산납(CH3COOPbㆍ3H2O), 질산납(Pb(NO3)2)등과 높은 융점을 갖는 산화지르코늄(ZrO2), 산화티타늄(TiO2), 산화티타늄납(PbTiO3), 산화지르코늄납(PbZrO3)등을 혼합 분쇄하는 공정과 스크린프린팅이 가능하게 하기위한 유기물질을 혼합하는 공정과 이러한 혼합공정을 통하여 스크린프린팅이 가능한 잉크를 제조하는 공정과, 잉크를 이용하여 원하는 기판위에 프린팅하는 공정과, 원료에 포함된 유기물을 제거하기위한 건조공정과, PZT를 형성시키기 위한 열처리 공정으로 구성된다.The present invention is a ZrO oxide having a high melting point with lead oxide (PbO), lead acetate (CH 3 COOPb · 3H 2 O), lead nitrate (Pb (NO 3 ) 2 ) and the like as a starting material for forming PZT 2 ), mixing and grinding titanium oxide (TiO 2 ), lead titanium oxide (PbTiO 3 ), lead zirconium oxide (PbZrO 3 ), mixing organic materials to enable screen printing, and mixing It consists of a process of manufacturing ink which can be screen printed through, a process of printing on a desired substrate using the ink, a drying process for removing organic matter contained in the raw material, and a heat treatment process for forming PZT.
첨부한 도면을 참조하여 본 발명을 상세히 설명한다.The present invention will be described in detail with reference to the accompanying drawings.
도 1은 본 발명에 따른 부분용융을 이용한 PZT 후막의 제조공정도이다. 본 발명은 낮은 융점을 갖는 물질로서 산화납(PbO), 초산납(CH3COOPbㆍ3H2O), 질산납(Pb(NO3)2)등과 높은 융점을 갖는 물질로서 산화지르코늄(ZrO2), 산화티타늄(TiO2), 산화티타늄납(PbTiO3), 산화지르코늄납(PbZrO3)등을 출발물질로 하여 Pb1+x(ZryTi1-y)O3조성을 갖도록 배합하여 볼밀 등의 방법으로 혼합분쇄 한다. 이때 x는 0에서 0.3의 범위를 가지며, y는 0.3에서 0.7 범위를 갖는다. 한편 PZT는 이력특성 및 변위특성 등을 개선하기 위하여 La, Mg, Nb, Sr, Mn 등의 물질을 도핑하여 사용할 수도 있다. 혼합분쇄된 원료분말과 유기물질로서 폴리에틸렌 글리콜(Polyethylene glycol), 알파-테피네올(α-tepineol), 폴리비닐 부티랄(Polyvinyl butyral), 부톡시 에톡시 에틸 아세테이트(Butoxy etoxy ethyl acetate)등 4종류의 혼합물을 무게비로 3:7∼7:3의 비율로 혼합하고 믹서로 30분간 혼합하여 스크린프린팅용 잉크를 제조한다. 제조된 잉크를 사용하여 실크스크린프린팅 등의 방법으로 기판에 프린팅 한다.1 is a manufacturing process of the PZT thick film using the partial melting according to the present invention. The present invention is a material having a high melting point with lead oxide (PbO), lead acetate (CH 3 COOPb · 3H 2 O), lead nitrate (Pb (NO 3 ) 2 ), etc. as a material having a low melting point, zirconium oxide (ZrO 2 ), Titanium oxide (TiO 2 ), lead titanium oxide (PbTiO 3 ), lead zirconium oxide (PbZrO 3 ) and the like as a starting material to be formulated to have a Pb 1 + x (Zr y Ti 1-y ) O 3 composition method such as ball mill Mix and grind. X has a range of 0 to 0.3, and y has a range of 0.3 to 0.7. The PZT may be doped with materials such as La, Mg, Nb, Sr, and Mn to improve hysteresis and displacement characteristics. As mixed raw powder and organic substance, polyethylene glycol, alpha-tepineol, polyvinyl butyral, butoxy ethoxy ethyl acetate, etc. 4 Mixtures of different types were mixed in a ratio of 3: 7 to 7: 3 by weight and mixed for 30 minutes with a mixer to prepare an ink for screen printing. The prepared ink is printed on the substrate by a method such as silk screen printing.
프린팅된 기판을 50℃에서 600℃ 범위에서 건조하여 유기물을 제거한다. 이때 건조온도는 사용된 저융점 원료의 융점보다는 낮고 사용된 유기물질의 분해온도 보다는 높은 온도로 한다. 참고로 저융점 원료의 융점을 열거하면 초산납은 75℃, 질산납은 400℃, 산화납은 880℃이며 유기물질의 분해온도는 60∼500℃이다. 따라서 유기물의 제거를 위한 건조는 50∼600℃ 범위의 온도가 바람직하다.The printed substrate is dried at 50 ° C to 600 ° C to remove organics. At this time, the drying temperature is lower than the melting point of the low melting point raw material used and higher than the decomposition temperature of the used organic material. For reference, the melting point of low-melting raw materials is listed. Lead acetate is 75 ℃, lead nitrate is 400 ℃, lead oxide is 880 ℃ and decomposition temperature of organic material is 60 ~ 500 ℃. Therefore, the drying for removal of organic matter is preferably in the temperature range of 50 to 600 ℃.
건조된 기판을 PZT 생성반응 및 저융점 원료의 액상이 형성되도록 600℃에서 1,000℃ 범위의 온도에서 열처리한다. 상기 공정을 통하여 PZT 후막을 기판 위에 형성한다.The dried substrate is heat-treated at a temperature in the range of 600 ° C. to 1,000 ° C. to form a PZT reaction and a liquid phase of a low melting point raw material. Through the above process, a PZT thick film is formed on the substrate.
도 2는 Si 웨이퍼 위에 Pt(백금)전극이 증착된 기판위에 본 발명으로 제조한 PZT 후막의 XRD(X-ray diffractometer) 그래프이다. 도2에서와 같이 모든 XRD 피크들이 PZT와 Si 그리고 Pt 성분만으로 이루어진 것을 알 수 있으며, 본 발명으로 제조한 후막은 완전한 PZT로 결정화 되었음을 알 수 있다.2 is an X-ray diffractometer (XRD) graph of a PZT thick film prepared by the present invention on a substrate on which a Pt (platinum) electrode is deposited on a Si wafer. As shown in FIG. 2, it can be seen that all XRD peaks are composed of only PZT, Si, and Pt components, and the thick film prepared according to the present invention is crystallized to complete PZT.
도 3(a)는 본 발명의 원료를 사용하여 750℃에서 제조한 PZT 후막의 단면 및 표면을 기울여서 SEM(Scanning electron microscope)으로 관찰한 사진으로 20㎛정도의 두께를 갖는 후막이 균일하게 제조되었음을 알 수 있다. 도 3(b)는 동일하게 제조한 PZT 후막의 단면을 40,000배의 고배율로 관찰한 SEM 사진이다. 750℃의 저온에서 소결하여도 치밀하고 미세한 입자분포를 가지고 있음을 알 수 있다.Figure 3 (a) is a photograph observed with a scanning electron microscope (SEM) by tilting the cross-section and surface of the PZT thick film prepared at 750 ℃ using the raw material of the present invention that the thick film having a thickness of about 20㎛ uniformly produced Able to know. FIG. 3 (b) is a SEM photograph of a 40,000-fold high magnification of the section of the PZT thick film prepared in the same manner. It can be seen that even when sintered at a low temperature of 750 ℃ has a fine and fine particle distribution.
본 발명은 PZT를 구성하는 원료만을 사용하여 1,000℃ 이하의 낮은 온도에서 열처리하여 PZT를 형성시킴으로써 충분한 소결밀도를 가지며 소결 후 균일하고 미세한 입자들로 형성되므로 종래의 소결조제를 사용하여 제조하는 방법에 비하여 불순물의 영향을 받지 않는 우수한 압전 및 유전특성을 갖을 뿐만 아니라 반응시간이 짧기 때문에 경제적으로 PZT 후막을 제조할 수 있다.The present invention has a sufficient sintered density by heat treatment at a low temperature of less than 1,000 ℃ using only the raw material constituting the PZT to form a PZT and is formed into uniform and fine particles after sintering in the method using a conventional sintering aid Compared with the excellent piezoelectric and dielectric properties which are not affected by impurities as well as the short reaction time, PZT thick films can be economically manufactured.
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KR100492935B1 (en) * | 2002-11-15 | 2005-06-02 | 한국에너지기술연구원 | Low temperature sintering of piezoelectric element |
KR101006958B1 (en) * | 2008-12-12 | 2011-01-12 | 한국기계연구원 | Piezoelectric thick flim for sensor containing oragnic materials and method for preparing the same |
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KR100890006B1 (en) * | 2007-06-19 | 2009-03-25 | 한국기계연구원 | PZT based piezoelectric thick film containing organic materials and nano pore, and preparation method thereof |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100492935B1 (en) * | 2002-11-15 | 2005-06-02 | 한국에너지기술연구원 | Low temperature sintering of piezoelectric element |
KR101006958B1 (en) * | 2008-12-12 | 2011-01-12 | 한국기계연구원 | Piezoelectric thick flim for sensor containing oragnic materials and method for preparing the same |
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