KR20000075303A - Method for Preparing Metaloxide Fine Dispersion Slurry for CMP - Google Patents
Method for Preparing Metaloxide Fine Dispersion Slurry for CMP Download PDFInfo
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- KR20000075303A KR20000075303A KR1019990019822A KR19990019822A KR20000075303A KR 20000075303 A KR20000075303 A KR 20000075303A KR 1019990019822 A KR1019990019822 A KR 1019990019822A KR 19990019822 A KR19990019822 A KR 19990019822A KR 20000075303 A KR20000075303 A KR 20000075303A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
Abstract
Description
본 발명은 반도체소자 제조 공정중 화학적 기계적 연마(Chemical Mechanical Polishing : CMP) 공정에 사용되는 금속산화물 슬러리의 제조방법에 관한 것으로, 더욱 상세하게는 글리세린을 물에 첨가하고 -20∼20℃ 범위로 온도를 낮춘 후, 이 혼합온도를 유지하면서 금속산화물을 70㎏/h이하의 속도로 첨가,혼합함으로써 혼합액을 제조하는 단계를 포함하여 분산안정성 및 연마속도가 우수하고, μ-스크래치 발생율을 현저히 감소시킬 수 있는 CMP용 금속산화물 미세 분산 슬러리의 제조방법에 관한 것이다.The present invention relates to a method for producing a metal oxide slurry used in the chemical mechanical polishing (CMP) process of the semiconductor device manufacturing process, more specifically, to the temperature in the range of -20 ~ 20 ℃ by adding glycerin to water After lowering, while maintaining the mixing temperature, adding and mixing the metal oxide at a rate of 70 kg / h or less, to prepare a mixed solution, excellent dispersion stability and polishing rate, significantly reducing the rate of μ-scratch It relates to a method for producing a metal oxide fine dispersion slurry for CMP.
반도체 소자 제조공정 중 CMP공정은 반도체 소자를 제조할 때 사용하는 리토그래피(Lithography)의 일종으로, 반도체 소자가 점차 미세화 고밀도화 및 다층구조를 갖게 됨에 따라 기존의 SOG(spin-on-glass)나 에치백(Etchback) 방법으로는 이룰 수 없는 광역 평탄화에 사용되는 기술로서, 메모리 반도체는 64M 이상, 비메모리 반도체는 250MHz 이상부터는 필수적으로 적용해야 하는 공정이라 할 수 있다.CMP process of semiconductor device manufacturing process is a kind of lithography used to manufacture semiconductor devices. As semiconductor devices become increasingly finer and denser and have a multi-layer structure, existing SOG (spin-on-glass) or As a technology used for wide area planarization that cannot be achieved by the etching back method, the memory semiconductor is required to be applied from 64M or higher and the non-memory semiconductor from 250MHz or higher.
일반적으로 CMP공정에 사용되는 금속산화물 슬러리는 분산성이 양호하고, 우수한 연마속도를 가지며, 연마후 웨이퍼(wafer) 표면에 μ-스크래치등과 같은 결함이 적어야 하며 고순도일 것이 요구된다. 특히 CMP공정 중 웨이퍼 표면에 μ-스크래치를 발생시키면 이후 얕은 트렌치 분리(Shallow Trench Isolation)공정 중 반도체 소자의 수율이 감소하게 된다.In general, the metal oxide slurry used in the CMP process has good dispersibility, excellent polishing speed, low defects such as μ-scratch on the wafer surface after polishing, and high purity. In particular, when the micro-scratch is generated on the wafer surface during the CMP process, the yield of semiconductor devices is reduced during the shallow trench isolation process.
이와 같은 슬러리의 조건들 대부분은 모두 슬러리의 주성분인 금속산화물 입자크기 및 분포와 밀접한 관련이 있다. 즉, 금속산화물의 입자 크기가 작을수록 분산안정성이 양호하고 μ-스크래치가 감소되는 장점이 있고, 입자 분포는 좁고 균일하게 분포하는 것이 연마표면의 평탄도가 좋아지고, μ-스크래치가 감소하므로 바람직하다. 단, 입자 크기가 지나치게 작다면 연마속도가 느려지게 되어 생산성이 저하되므로 입자 크기는 너무 작지 않은 적정한 크기가 되어야 한다. 정리해 보면, CMP 공정용 슬러리는 연마속도, 분산안정성, μ-스크래치 등을 고려하여 적정 크기 및 분포를 갖는 슬러리가 요구된다고 할 수 있다.Most of these slurry conditions are closely related to the size and distribution of the metal oxide particles, which are the main components of the slurry. In other words, the smaller the particle size of the metal oxide is, the better the dispersion stability and the μ-scratch is reduced, the narrower and more uniform the particle distribution, the better the flatness of the polishing surface and the less the scratch is preferable. Do. However, if the particle size is too small, the polishing rate is slowed down and the productivity is lowered, so the particle size should be an appropriate size not too small. In summary, it can be said that the slurry for the CMP process requires a slurry having an appropriate size and distribution in consideration of polishing rate, dispersion stability, μ-scratch, and the like.
종래 알려져 있는 CMP용 금속산화물 슬러리의 제조방법으로, 미국 특허 제 5,382,272호에는 물, 금속산화물과 화학 첨가제가 혼합된 상태에서 비드(Bead)를 첨가한 후 다이노밀(Dynomill)또는 볼밀(Ballmill)로 고속 교반하는 방법이나 독일 이카사(IKA 社)의 물, 금속산화물과 화학첨가제가 혼합된 상태에서 로터(Rotor)로 유체를 고속회전시켜 스테이터(stator)에 충돌과 마찰을 일으키는 방법 등이 있다. 통상적인 제조방법에서 대개 금속산화물로는 실리카, 알루미나, 세리아, 지르코니아, 티타니아 등을 사용하고, 화학 첨가제로는 일반적으로 피연마 대상이 실리카 등의 절연층일 경우는 아민이나 수산화 칼슘 등의 염기성 물질을, 피연마 대상이 금속 배선이나 플러그 등의 금속층일 경우는 황산, 질산, 초산 등의 산 및 과산화 수소와 같은 산화제를 사용한다.A conventionally known method for producing a metal oxide slurry for CMP, U.S. Patent No. 5,382,272, which adds beads in a state in which water, metal oxides, and chemical additives are mixed, followed by a Dynomill or Ballmill. There is a method of high-speed stirring or a method of causing a high-speed rotation of the fluid in the rotor in a state where water, metal oxides and chemical additives of IKA, Germany, are mixed, causing collision and friction to the stator. In a conventional manufacturing method, silica, alumina, ceria, zirconia, titania, etc. are generally used as metal oxides, and chemical additives generally include basic materials such as amines and calcium hydroxides when the target layer to be polished is an insulating layer such as silica. When the object to be polished is a metal layer such as a metal wire or a plug, an acid such as sulfuric acid, nitric acid, acetic acid, and an oxidizing agent such as hydrogen peroxide are used.
이러한 기존의 방법들을 이용할 경우 금속 슬러리의 입자 크기 및 분포에 한계가 있다는 단점 외에도, 분산 전에 비해서 분산 후 금속산화물 입자의 크기가 감소하여 입자의 표면적이 증가함으로써 혼합액의 성질이 변화하는 문제점이 발생한다. 즉, 금속산화물을 상온에서 혼합하면 금속산화물 입자가 뭉쳐지면서 크기가 100∼1000배 정도 증가하고 이후 금속산화물을 분산시키면 금속산화물 입자가 다시 미립화되면서 입자의 표면적이 매우 크게 증가하게 된다. 이때 금속산화물 입자 표면의 증가된 화학 작용기가 화학 첨가제와 반응을 일으킴으로써 혼합액의 pH가 변하게 되고, 또 금속산화물 입자 표면의 포텐셜이 크게 변하게 되는데, 이러한 변화는 분산된 금속산화물이 다시 뭉쳐지거나 슬러리의 침강 안정성이 감소하는 등의 분산 효과의 감소로 이어지게 된다. 이와 같이 기존의 상온에서의 혼합 및 분산 방법에 의할 경우 분산 안정성이 좋지 않다는 단점 때문에, CMP공정에서 요구하는 초미립화된 금속산화물 슬러리를 제조하기에는 적합하지 않은 문제가 있었다.In addition to the drawbacks of using the conventional methods, the particle size and distribution of the metal slurry are limited. In addition, the size of the metal oxide particles decreases after dispersing compared to before dispersing, thereby increasing the surface area of the metal slurry, thereby changing the properties of the mixed solution. . That is, when the metal oxide is mixed at room temperature, the size of the metal oxide particles agglomerates and increases by about 100 to 1000 times, and when the metal oxide is dispersed thereafter, the metal oxide particles are re-atomized, thereby greatly increasing the surface area of the particles. At this time, the increased chemical functional groups on the surface of the metal oxide particles react with the chemical additives, thereby changing the pH of the mixed solution, and the potential of the surface of the metal oxide particles is greatly changed. This leads to a decrease in dispersion effect such as reduced sedimentation stability. As described above, due to the disadvantage of poor dispersion stability when mixing and dispersing at room temperature, there is a problem in that it is not suitable for producing the ultrafine metal oxide slurry required in the CMP process.
본 발명의 목적은 상기와 같은 종래의 문제점을 해결하기 위하여 안출된 것으로, 물과 금속산화물을 혼합하는 단게에서 금속산화물 입자가 뭉쳐 입자 크기가 증가하는 것을 최대한 억제하고, 이를 통해 이후의 분산 단계에서 분산 전후 입자 표면적의 변화를 감소시킴으로써, 분산 안정성이 좋은 CMP용 금속산화물 미세 분산 슬러리를 제조하는 방법을 제공하는 것이다. 이와 같은 본 발명의 목적은 물과 금속산화물을 혼합하는 단계에서 적정 첨가제를 사용하고, 혼합 온도 및 금속산화물 투입 속도를 적절히 제어함으로써 달성될 수 있다.An object of the present invention was devised to solve the conventional problems as described above, the metal oxide particles are aggregated in the step of mixing the water and the metal oxide to suppress the increase in the particle size as much as possible, through the subsequent dispersion step It is to provide a method for producing a metal oxide fine dispersion slurry for CMP having good dispersion stability by reducing the change of the particle surface area before and after dispersion. This object of the present invention can be achieved by using a suitable additive in the step of mixing the water and the metal oxide, and appropriately controlling the mixing temperature and the metal oxide input rate.
즉, 본 발명은 금속산화물 슬러리 제조시 분산화 단계 이전에 금속산화물과 수용액을 혼합하는데 있어서, 글리세린을 물에 첨가하고 -20∼20℃ 범위로 온도를 낮춘 후, 이 혼합온도를 유지하면서 금속산화물을 70㎏/h이하의 속도로 첨가,혼합함으로써 혼합액을 제조하는 단계를 포함하는 것을 특징으로 하는 CMP용 금속산화물 미세 분산 슬러리의 제조방법에 관한 것이다.That is, in the present invention, in the preparation of the metal oxide slurry, the metal oxide is mixed with an aqueous solution before the dispersing step, and glycerin is added to water and the temperature is lowered to -20 to 20 ° C., and then the metal oxide is maintained while maintaining the mixing temperature. It relates to a method for producing a metal oxide fine dispersion slurry for CMP comprising the step of preparing a mixed solution by adding and mixing at a rate of 70 kg / h or less.
이하, 본 발명에 대해 상세히 설명하고자 한다.Hereinafter, the present invention will be described in detail.
본 발명에서 사용할 수 있는 금속산화물은 실리카(SiO2), 알루미나(Al2O3), 세리아(CeO2), 지르코니아(ZrO2), 티타니아(TiO2) 등으로 발연법이나 졸겔법(Sol-Gel법) 등으로 만들어진 것 어느 것이나 사용 가능하다. 이들 금속산화물의 입자크기는 10∼100㎚이며, 바람직하게는 20∼60㎚인 경우가 좋다. 금속산화물의 평균 입자 크기가 10㎚ 미만으로 너무 작으면 연마속도가 떨어져 생산성 측면에서 바람직하지 못하고, 반대로 평균 입자 크기가 100㎚ 를 초과할 경우 분산이 어려워지며 μ-스크래치를 다량 유발하는 원인이 된다. 이들 금속산화물들을 수용액에 분산시킨 후에는 입자의 평균 크기가 20∼250㎚인 것이 바람직하고, 미량이라도 500㎚ 이상의 입자가 존재하면 침강안정성이 떨어지고, μ-스크래치를 유발하게 되므로 좋지 않다.Metal oxides that can be used in the present invention are silica (SiO 2 ), alumina (Al 2 O 3 ), ceria (CeO 2 ), zirconia (ZrO 2 ), titania (TiO 2 ) and the like fume or sol-gel method (Sol- Any one made with the Gel method) can be used. The particle size of these metal oxides is 10 to 100 nm, preferably 20 to 60 nm. If the average particle size of the metal oxide is too small, less than 10 nm, the polishing rate is unfavorable in terms of productivity, on the contrary, if the average particle size exceeds 100 nm, dispersion becomes difficult and causes a large amount of μ-scratches. . After dispersing these metal oxides in an aqueous solution, it is preferable that the average size of the particles is 20 to 250 nm, and even if a small amount of particles of 500 nm or more is present, sedimentation stability is lowered, causing micro-scratches.
상기와 같은 금속산화물을 고형물 농도 5∼50중량% 범위가 되도록 혼합하는 것이 바람직한데, 혼합액 중 고형물의 농도가 5중량% 미만인 경우에는 슬러리의 연마 성능이 만족스럽지 못하게 되고, 50중량%를 초과하는 경우에는 틱소트로피(Thixotropy)현상으로 인하여 점도가 급격히 증가하게 되어 바람직하지 못하게된다.It is preferable to mix such metal oxides so as to have a solid concentration in the range of 5 to 50% by weight. When the concentration of solids in the mixed liquid is less than 5% by weight, the polishing performance of the slurry becomes unsatisfactory and exceeds 50% by weight. In this case, the viscosity increases rapidly due to thixotropy, which is undesirable.
본 발명에서는 화학 첨가제로 글리세린을 사용하게 되는데, 이 물질은 금속산화물의 첨가 및 혼합시 발생되는 혼합액의 온도 변화를 완충하는 작용을 한다. 또한 본 발명에서는 글리세린과 함께 에틸렌글리콜을 추가로 사용할 수도 있는데, 에틸렌글리콜은 CMP 연마시에 간혹 존재하는 거대 입자와 피연마 재질 사이에서 윤활 작용을 함으로써 피연마 재질의 μ-스크래치를 줄이는 역할을 한다. 본 발명에서는 상기의 글리세린과 에틸렌글리콜을 합하여 0.05∼0.5중량%의 범위에서 첨가하는 것이 바람직하다. 이들 화학 첨가제의 첨가량이 0.05중량% 미만이면 그 효과를 기대하기가 어렵고, 0.5중량%를 초과하면 슬러리의 연마성능이 감소하거나 거품이 발생할 수 있으므로 좋지 않다.In the present invention, glycerin is used as a chemical additive, and this material serves to buffer the temperature change of the mixed solution generated when the metal oxide is added and mixed. In addition, in the present invention, ethylene glycol may be additionally used together with glycerin, and ethylene glycol serves to reduce the μ-scratch of the polished material by lubricating between the large particles and the polished material which are sometimes present during CMP polishing. . In this invention, it is preferable to add said glycerin and ethylene glycol in the range of 0.05 to 0.5 weight%. If the added amount of these chemical additives is less than 0.05% by weight, it is difficult to expect the effect, and when it exceeds 0.5% by weight, it is not good because the polishing performance of the slurry may decrease or foaming may occur.
본 발명에서는 산, 염기 또는 산화제를 첨가제로서 사용할 수 있는데, 피연마 대상이 실리카 등의 절연층일 때는 아민이나 수산화 칼슘 등의 염기성 첨가제를 사용하며, 금속 배선이나 플러그 등 금속층을 연마시에는 황산, 질산, 초산 등의 산 및 과산화수소와 같은 산화제를 사용할 수 있다.In the present invention, an acid, a base, or an oxidizing agent may be used as an additive. When the target to be polished is an insulating layer of silica or the like, a basic additive such as amine or calcium hydroxide is used, and sulfuric acid or nitric acid is used to polish metal layers such as metal wires or plugs. Acids such as, acetic acid, and oxidizing agents such as hydrogen peroxide can be used.
본 발명에서는 물과 화학 첨가제를 혼합하여 수용액을 제조하고 금속산화물을 투입하기 이전에 수용액의 온도를 -20∼20℃로 낮추게 되며, 금속산화물을 투입하여 혼합하는 중에서도 이러한 온도범위를 유지하여야 한다. 일반적으로 금속산화물을 혼합할 때 발열반응이 일어나므로, 혼합액의 온도를 낮게 유지할수록 혼합이 원활하게 이루어져 혼합 후 금속산화물 입자의 평균 크기가 줄어드는 경향을 보인다. 다만, 혼합 온도가 20℃를 초과하면 본 발명에서 목적하는 입자의 미세 분산이 어려워 지고, -20℃ 미만이면 제조비용과 방법의 편의성 측면에서 바람직하지 않다.In the present invention, water and chemical additives are mixed to prepare an aqueous solution, and before the metal oxide is added, the temperature of the aqueous solution is lowered to -20 to 20 ° C., and this temperature range should be maintained even during mixing by adding the metal oxide. In general, since the exothermic reaction occurs when the metal oxide is mixed, the lower the temperature of the mixed solution, the smoother the mixing is, the average size of the metal oxide particles after mixing tends to decrease. However, when the mixing temperature is more than 20 ° C it becomes difficult to finely disperse the particles desired in the present invention, less than -20 ° C is not preferable in terms of manufacturing cost and convenience of the method.
본 발명에서는 -20∼20℃로 유지된 수용액에 금속산화물을 투입하게 되는데, 그 투입속도를 70㎏/h 이하로 유지하여 혼합하게 된다. 70㎏/h를 초과할 경우 본 발명에서 기대하는 미세 분산 슬러리를 제조하기 어려워지기 때문으로, 더욱 바람직하게는 10㎏/h 이하로 유지하는 것이 좋다. 금속산화물을 수용액에 투입하는 중에 혼합이 계속해서 이루어져야 하고, 이를 위한 반응기의 교반 속도는 금속산화물의 첨가 속도와는 무관하게 100rpm정도로 유지하는 것이 좋다.In the present invention, the metal oxide is added to the aqueous solution maintained at -20 to 20 ° C, and the mixing rate is maintained at 70 kg / h or less. When it exceeds 70 kg / h, since it becomes difficult to manufacture the fine dispersion slurry expected by this invention, it is good to keep it at 10 kg / h or less more preferably. While the metal oxide is added to the aqueous solution, the mixing should be continued, and the stirring speed of the reactor is preferably maintained at about 100 rpm regardless of the addition rate of the metal oxide.
지금까지 설명한 바와 같이, 본 발명에서는 금속산화물을 분산하는 과정 이전에 수용액상 혼합액을 제조하는 단계에 있어서, 적정한 화학 첨가제를 사용하고, 혼합 온도 및 금속산화물의 투입 속도를 적절하게 제어함으로써, 혼합액내의 금속산화물의 평균 입자 크기가 작은 혼합액을 제조할 수 있게 된다. 따라서, 이후 분산 공정에서 상기 혼합액을 미립화 분산시킬 경우, 분산 전후의 금속산화물 입자 크기 변화가 기존의 방법, 즉 상온에서 혼합 후 분산한 금속산화물 입자 크기 변화와 비교할 때 상대적으로 차이가 작게 된다.As described above, in the present invention, in the step of preparing an aqueous solution mixture before the process of dispersing the metal oxide, by using a suitable chemical additive, by appropriately controlling the mixing temperature and the metal oxide injection rate, It is possible to prepare a mixed liquid having a small average particle size of the metal oxide. Accordingly, when the mixed solution is atomized and dispersed in a subsequent dispersion process, the change in the size of the metal oxide particles before and after the dispersion becomes relatively small compared with the conventional method, that is, the change in the size of the metal oxide particles dispersed after mixing at room temperature.
본 발명에 있어서, 금속산화물을 분산하는 방법으로는 통상의 분산방법을 이용하므로 밀링(Milling)방법이나 하이믹싱(Hi-mixing) 또는 유체충돌방법을 모두 쓸 수 있다. 이중 대향충돌방법(대한민국 특허출원 제 98-39212호)을 사용하여 분산액을 제조하는 예를 들어 보면, 상기의 방법에 의해 제조된 금속산화물 혼합액을 펌프를 통하여 분산챔버로 이송하고, 고압을 가하여 대향하고 있는 2개의 오리피스로부터 대향 충돌시켜 분산시킨다.In the present invention, since a conventional dispersion method is used as the method for dispersing the metal oxide, both a milling method, a hi-mixing method, or a fluid collision method can be used. For example, to prepare a dispersion using a double opposing collision method (Korean Patent Application No. 98-39212), the metal oxide mixture prepared by the above method is transferred to the dispersion chamber through a pump, and the high pressure is applied to face the dispersion. The two colleted orifices face each other and are dispersed.
본 발명에 의해 최종적으로 수득되는 금속산화물 분산액은 분산 전후 금속산화물 입자의 표면적 변화 차이가 작아, 분산 후 제조된 CMP용 슬러리의 pH변화가 심하지 않으며, 포텐셜의 변화도 상대적으로 작아져 분산 후 다시 뭉치거나 슬러리의 불안정으로 인하여 침강하는 현상이 적어진다.The metal oxide dispersion finally obtained by the present invention has a small difference in the surface area change of the metal oxide particles before and after dispersion, so that the pH change of the slurry for CMP prepared after dispersion is not severe, and the potential change is also relatively small, so that after the dispersion Or less settling due to instability of the slurry.
이하, 본 발명을 실시예를 들어 더욱 상세히 설명하고자 하나 본 발명이 하기 실시예에 의하여 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.
실시예 1Example 1
혼합용 반응기에서 순수한 물과 20%-KOH용액 90g, 글리세린 10g 그리고 에틸렌글리콜 10g을 혼합하고 온도를 -20℃로 냉각하였다. 온도가 계속 유지되는 위 수용액에 시판되는 실리카(데구사(Degussa)社의 Aerosil 200 : 표면적 200㎡/g) 500g을 투입 속도 10㎏/h로 하여 투입하고, 100rpm으로 교반하였다. 이후 이 혼합액을 이송펌프(Diaphram 1-50기압) 및 고압펌프(Intensifier 50-1500기압)를 통하여 입구직경이 0.4㎜이고 출구직경이 0.2㎜이며 세라믹 재질의 오리피스가 2개 설치된 분산챔버로 이송하고 500기압에서 대향충돌시켜 분산시켰다. 분산챔버를 통과하여 나온 분산액은 입도분석기(Zetasizer, Malvern사)를 이용하여 입자 크기 분포를 측정하여 표 1에 나타내었다. 또한 분산액을 제조하고 6개월 후에 연마성능 테스트를 실시하였다. 연마성능 테스트 방법은 다음과 같다.In a reactor for mixing, pure water and 90 g of 20% -KOH solution, 10 g of glycerin and 10 g of ethylene glycol were mixed and the temperature was cooled to -20 ° C. 500 g of commercially available silica (Aerosil 200 from Degussa: surface area 200 m 2 / g) was added at an input rate of 10 kg / h, and stirred at 100 rpm. Then, the mixed liquid is transferred to a dispersion chamber having a diameter of 0.4 mm, an outlet diameter of 0.2 mm, and two ceramic orifices installed through a transfer pump (Diaphram 1-50 atm) and a high pressure pump (Intensifier 50-1500 atm). Disperse | distribute by opposing collision at 500 atmosphere. Dispersion solution passed through the dispersion chamber is shown in Table 1 by measuring the particle size distribution using a particle size analyzer (Zetasizer, Malvern). In addition, the polishing performance test was carried out 6 months after the dispersion was prepared. Polishing performance test method is as follows.
▶연마성능 테스트 방법◀▶ Abrasive Performance Test Method ◀
○ 연마 기기는 6EC(STRASBAUGH사)를 사용하였고, 웨이퍼는 P-TEOS를 도포한 6인치 배어웨이퍼(Bare Wafer)를 사용하였다.The polishing machine used 6EC (STRASBAUGH) and the wafer used the 6-inch bare wafer coated with P-TEOS.
○ 연마 조건○ Polishing condition
- 패드 타입(Pad type) : IC1000/Suba Ⅳ Stacked (Rodel사)-Pad type: IC1000 / Suba Ⅳ Stacked (Rodel)
- 플레이튼 스피드(Platen Speed) : 120rpmPlaten Speed: 120 rpm
- 퀼 스피드(Quill Speed) : 120rpmQuill Speed: 120rpm
- 프레셔(Pressure) : 7psi-Pressure: 7psi
- 백 프레셔(Back Pressure) : 0psi-Back Pressure: 0psi
- 온도 : 25℃Temperature: 25 ℃
- 슬러리 유량 : 150㎖/min-Slurry flow rate: 150ml / min
○ 상기 조건에서 각각의 슬러리를 이용하여 2분간 연마를 실시한 후, 연마 전후의 두께 변화로부터 연마 속도를 측정하였으며, μ-스크래치는 KLA(TENCOR사)기기를 이용하여 측정하였다. 웨이퍼의 평탄도는 WIWNU로 나타내었는데, 그 산출방법은 다음식에 의한다.After polishing for 2 minutes with each slurry under the above conditions, the polishing rate was measured from the thickness change before and after polishing, and the μ-scratch was measured using a KLA (TENCOR company) instrument. The flatness of the wafer is represented by WIWNU, and the calculation method is based on the following equation.
단, STD.는 웨이퍼 부분별로 식각된 양의 표준편차를 뜻하고, R.R.은 웨이퍼 전체의 식각속도를 말한다.However, STD. Refers to the standard deviation of the amount etched by each wafer portion, and R.R. refers to the etching rate of the entire wafer.
각각의 슬러리에 대한 연마성능 결과는 아래 표 2에 나타내었다.Abrasive performance results for each slurry are shown in Table 2 below.
실시예 2∼12Examples 2-12
혼합 온도, 금속산화물 투입 속도, 에틸렌글리콜 첨가여부를 표 1과 같이 변화시킨 것을 제외하고는 실시예 1과 동일한 방법으로 실시하여 그 결과를 표 1 및 표 2에 나타내었다.Except that the mixing temperature, the metal oxide input rate, ethylene glycol addition was changed as shown in Table 1 was carried out in the same manner as in Example 1 and the results are shown in Table 1 and Table 2.
실시예 13∼24Examples 13-24
실리카 대신 세리아(CeO2: 표면적 30㎡/g)를 사용하고 혼합 온도, 금속산화물 투입 속도, 에틸렌글리콜 첨가 여부를 표 1과 같이 변화시킨 것을 제외하고는 실시예 1과 동일한 방법으로 실시하여 그 결과를 표 1 및 표 2에 나타내었다.The result was carried out in the same manner as in Example 1 except that ceria (CeO 2 : surface area 30 m 2 / g) was used instead of silica, and the mixing temperature, metal oxide input rate, and ethylene glycol addition were changed as shown in Table 1. Are shown in Table 1 and Table 2.
비교예 1Comparative Example 1
글리세린 및 에틸렌글리콜을 첨가하지 않고 혼합온도를 상온(25℃)로 하였으며 금속산화물을 1회적으로 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하여 그 결과를 표 1 및 표 2에 나타내었다.The mixing temperature was adjusted to room temperature (25 ° C) without the addition of glycerin and ethylene glycol, and the results were shown in Table 1 and Table 2, except that the metal oxide was added once. .
비교예 2Comparative Example 2
실리카 대신 세리아(CeO2: 표면적 30㎡/g)를 사용하고, 글리세린 및 에틸렌글리콜의 첨가없이 혼합온도를 상온(25℃)로 하였으며 금속산화물을 1회적으로 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하여 그 결과를 표 1 및 표 2에 나타내었다.Ceria (CeO 2 : surface area 30㎡ / g) was used instead of silica, and the mixing temperature was maintained at room temperature (25 ° C.) without addition of glycerin and ethylene glycol, except that the metal oxide was added once. It carried out by the same method and shows the result in Table 1 and Table 2.
이상에서 살펴본 바와 같이 본 발명에 의해 제조된 금속산화물 슬러리는 분산 전후의 금속산화물 입자의 표면적 변화가 작으므로, 분산이 보다 용이하고, 분산 후 제조된 CMP용 슬러리의 입자가 다시 뭉치는 현상이 감소하며, 슬러리의 불안정으로 침강하는 현상이 적어지므로, 슬러리내에서 금속산화물 입자가 미세 분산되어 CMP공정시 연마되는 웨이퍼 표면의 μ-스크래치가 감소하고 연마 균일성이 향상되어 반도체 소자 CMP용으로 유용한 금속 슬러리를 제조할 수 있다.As described above, since the metal oxide slurry prepared by the present invention has a small surface area change of the metal oxide particles before and after dispersion, the metal oxide slurry is more easily dispersed, and the particles of the CMP slurry prepared after dispersion are reduced again. In addition, since the sedimentation due to the instability of the slurry is reduced, the metal oxide particles are finely dispersed in the slurry, and the micro-scratch on the surface of the wafer polished during the CMP process is reduced and the polishing uniformity is improved, which is useful for semiconductor device CMP. Slurries can be prepared.
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990019822A KR100299162B1 (en) | 1999-05-31 | 1999-05-31 | Method for Preparing Metaloxide Fine Dispersion Slurry for CMP |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990019822A KR100299162B1 (en) | 1999-05-31 | 1999-05-31 | Method for Preparing Metaloxide Fine Dispersion Slurry for CMP |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20000075303A true KR20000075303A (en) | 2000-12-15 |
| KR100299162B1 KR100299162B1 (en) | 2001-11-05 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019990019822A KR100299162B1 (en) | 1999-05-31 | 1999-05-31 | Method for Preparing Metaloxide Fine Dispersion Slurry for CMP |
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| Country | Link |
|---|---|
| KR (1) | KR100299162B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100570122B1 (en) * | 2003-05-12 | 2006-04-11 | 학교법인 한양학원 | Slurry composition for chemical mechanical polishing capable of compensating nanotopography effect and method of planarizing surface of semiconductor device using the same |
-
1999
- 1999-05-31 KR KR1019990019822A patent/KR100299162B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100570122B1 (en) * | 2003-05-12 | 2006-04-11 | 학교법인 한양학원 | Slurry composition for chemical mechanical polishing capable of compensating nanotopography effect and method of planarizing surface of semiconductor device using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100299162B1 (en) | 2001-11-05 |
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