KR20010069578A - Method for growing the zy-quartz crystal - Google Patents

Method for growing the zy-quartz crystal Download PDF

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KR20010069578A
KR20010069578A KR1020010020858A KR20010020858A KR20010069578A KR 20010069578 A KR20010069578 A KR 20010069578A KR 1020010020858 A KR1020010020858 A KR 1020010020858A KR 20010020858 A KR20010020858 A KR 20010020858A KR 20010069578 A KR20010069578 A KR 20010069578A
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crystal
autoclave
temperature
growing
axis
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KR1020010020858A
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Korean (ko)
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이덕호
손재봉
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이덕호
에이비씨전자 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/08—Reaction chambers; Selection of materials therefor
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/16—Controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

PURPOSE: Disclosed is a method for growing zy-crystal to remove fine defect that exists in seed crystal surface and growth region by fixing proper temperature range, pressure range, condition of additive to deposit Si element in the mixed aqueous solution without forming unnecessary compound, to grow single crystal of identical quality for short time. CONSTITUTION: The method for growing zy-crystal is characterized by placing natural fertilization material in the lower end part of autoclave; locating plate seed crystal of revolution angle 00'00"(0001) from z axis to y axis on the basis of x axis in the upper end part(crystal growing part) after placing convection control plate(baffle); sealing the autoclave after filling by inputting solution for hydrothermal method containing sodium hydroxide into the autoclave; dropping temperature of the upper end part and raising temperature of the lower end part; depositing Si element with convective phenomenon as maintaining for constant term by controlling pressure. The solution for hydrothermal method contains LiOH and NaNO2. The temperature of the upper end part is maintained with 350deg.C or higher and internal pressure of the autoclave is maintained with 1800bar or higher.

Description

지와이-크리스탈의 성장방법{Method for growing the zy-quartz crystal}Method for growing the zy-quartz crystal

본 발명은 zy-크리스탈(zy-Crystal)의 성장방법에 관한 것으로, 좀 더 상세하게는 고온 및 고압 조건하에서 zy-크리스탈의 성장시 사용되는 수열용액을 변화시켜 제조상 발생할 수 있는 결함들이 제거하고 품질이 균일하여 진동자 및 공진자 뿐만 아니라 필터(Filter)용 등 여러 분야에 적용이 가능한 zy-크리스탈의 성장방법에 관한 것이다.The present invention relates to a growth method of zy-crystal (zy-crystal), and more particularly, to change the hydrothermal solution used during the growth of zy-crystal under high temperature and high pressure conditions to remove defects that may occur in manufacturing and quality The present invention relates to a method of growing zy-crystal, which is uniform and applicable to various fields such as not only a vibrator and a resonator but also a filter.

zy-크리스탈(zy-Crystal)이라 함은 일반적인 형태의 석영(Ouartz) 단결정이며, zy(밀러면 지수: (0001)인 종자판을 사용하여 z축으로 성장된 크리스탈 제조의 원료로 사용되는 공업적으로 육성된 고순도의 SiO2단결정을 의미한다.Zy-Crystal is a general type of quartz monocrystal, and is used as a raw material for the production of crystals grown on the z-axis using a seed plate with zy (Mill surface index: (0001). It means a high purity SiO 2 single crystal grown by.

현재 수정 디바이스(Device)의 수요는 상당히 많으며, zy-크리스탈의 생산량 또한 상당히 많다. 그리고 최근에는 전자 부품용으로 사용되는 zy-크리스탈의 제조방법이 다양하게 연구되고 있는 추세이다.Current demand for quartz devices is high, and the output of zy-crystals is also high. In recent years, a variety of researches have been carried out on methods of manufacturing zy-crystals used for electronic components.

예를 들어, 상기 석영 단결정의 육성을 위해 사용하는 종자결정판의 제조방법으로 미국특허 제5,714,005호 및 제6,001,171호 등이 있다. 상기 특허들에서는 39°내지 55°의 회전각을 갖는 석영 결정바(bar)로부터 절단된 판을 갖는 시드(seed)가 기재되어 있다. 그러나, 상기 특허들은 종자 결정판에 관련된 기술이며, zy-크리스탈의 성장에 관한 직접적인 공정에 대하여는 선행 특허 및 문헌 등이 없는 실정이다.For example, US Pat. Nos. 5,714,005 and 6,001,171, etc., are methods for producing seed crystal plates used for the growth of the quartz single crystal. The patents describe seeds having plates cut from quartz crystal bars with rotation angles between 39 ° and 55 °. However, the above patents are technologies related to seed crystallization, and there is no prior patent and literature regarding a direct process on the growth of zy-crystal.

한편, 현재까지 당업계에 알려져 있는 zy-크리스탈의 제조방법은 여러가지 문제점들이 내재되어 있다. 첫째, 비교적 높지 않은 온도(340℃이하)와 압력(1500bar이하) 조건하에서 zy-크리스탈을 성장시키기 때문에 생산효율이 낮다. 둘째, 비교적 낮은 압력하에서 zy-크리스탈을 성장시키기 때문에 단결정 내부에 불순물(Inclusion)이 많이 함유될 수 있다. 따라서 전자부품용으로 사용할 때 불량원인 되는 경우가 많이 발생하였다.On the other hand, there are various problems inherent in the production of zy-crystals known in the art to date. First, production efficiency is low because zy-crystals are grown under relatively high temperature (below 340 ° C) and pressure (below 1500bar). Second, since the zy-crystal is grown under relatively low pressure, a large amount of impurities may be contained in the single crystal. Therefore, when used for electronic components, a lot of cases are a cause of failure.

즉, 도 2 및 도 3을 참조하면, 상기 zy-크리스탈 단결정의 육성을 위해 사용하는 종래의 제조방법에서는 각각 성장 온도가 338℃ 이하와 340℃이하, 그리고 압력의 경우는 각각 1500bar이하 및 1200bar 이하에서 제조되고 있어, 부품으로 사용시에 불량원인으로 작용 될 소지가 있고, 생산성이 떨어지는 단점들이 있다. 참고적으로, 도 2는 일본 기업들이 채택하고 있는 zy-크리스탈 제조시의 온도 조건을 나타낸 그래프이며, 도 3은 러시아 기업들이 채택하고 있는 zy-크리스탈 제조시의 온도 조건을 나타낸 그래프이다. 도 2의 경우, zy-크리스탈의 고체 불순물 순위는 I이고, 단결정 두께는 약 16mm이며, 〈+X〉영역 생성비율은 34%이고, 생선성은 약 62% 정도이며, 도 3의 경우, zy-크리스탈의 고체 불순물 순위는 Ib이고, 단결정 두께는 약 18mm이며, 〈+X〉영역 생성비율은 38%이고, 생선성은 약 59% 정도이다. 각 측정항목에 대한 정의는 하기 표 1에 기재하였다.That is, referring to Figures 2 and 3, in the conventional manufacturing method used for the growth of the zy-crystal single crystal growth temperature is 338 ℃ or less and 340 ℃ or less, respectively, the pressure of 1500 bar or less and 1200 bar or less, respectively Because it is manufactured in, there is a possibility that it may act as a cause of failure when used as a part, there are disadvantages that productivity is low. For reference, FIG. 2 is a graph showing temperature conditions in zy-crystal manufacturing adopted by Japanese companies, and FIG. 3 is a graph showing temperature conditions in zy-crystal manufacturing adopted by Russian companies. In the case of Figure 2, the solid impurity rank of zy-crystal is I, the single crystal thickness is about 16mm, the <+ X> region formation rate is 34%, the fish is about 62%, and in Figure 3, zy- The solid impurity rank of the crystal is Ib, the single crystal thickness is about 18 mm, the ratio of <+ X> region formation is 38%, and the fish is about 59%. Definitions for each measurement item are shown in Table 1 below.

이에 본 발명자들은 이러한 종래의 문제점을 해결하기 위하여 광범위한 연구를 수행한 결과, zy-크리스탈의 성장 온도와 압력을 변하시키고, 수열용액에 첨가제를 부가함으로써 석영(Ouartz) 디바이스용 zy-크리스탈의 생산성 향상과 불량원인의 제거할 수 있었고, 본 발명은 이에 기초하여 완성되었다.Accordingly, the present inventors have conducted extensive research to solve the conventional problems, and as a result, the productivity of zy-crystal for quartz devices is improved by changing the growth temperature and pressure of the zy-crystal and adding an additive to the hydrothermal solution. And the cause of the failure can be eliminated, the present invention was completed based on this.

따라서, 본 발명의 목적은 혼합 수용액 내에서 Si원소가 불필요한 화합물의 생성없이 증착할 수 있는 적정한 온도 범위와 압력범위, 및 첨가물의 조건을 구명함으로써 종자결정 표면과 성장영역에 존재하는 미세결함을 제거하고, 동일한 품질의 단결정을 단기간에 성장시킬 수 있는 방법을 제공하는데 있다.Accordingly, an object of the present invention is to eliminate the microdefects present on the seed crystal surface and the growth region by determining the appropriate temperature and pressure ranges and the conditions of the additives which can be deposited without the formation of compounds without Si elements in the mixed aqueous solution. In addition, to provide a method for growing a single crystal of the same quality in a short time.

상기 목적을 달성하기 위한 본 발명의 zy-크리스탈의 성장방법은 천연 수정원료를 오토클래이브의 하단부(원료용해부)에 장착하고 대류조절판을 얹은 후 x축을 기준으로 z축에서 y축으로 회전각 00°00′(0001)인 판상 종자 결정을 상단부(결정 육성부)에 위치시킨 후, 수산화나트륨을 포함하는 수열용액을 상기 오토클래이브에 투입하여 충진시킨 후 오토클래이브를 밀봉시킨 다음, 상단부 온도를 강하시키고 하단부 온도를 승온시키며 압력을 조절하여 일정기간동안 유지시키면서 대류현상에 의한 Si원소의 증착을 이용한 석영 디바이스용 zy-크리스탈의 성장방법에 있어서, 상기 수열용액이 LiOH 및 NaNO2를 더욱 포함하며, 상기 상단부의 온도를 350℃ 이상으로 유지시키고, 상기 오토클래이브의 내부압력을 1800bar 이상으로 유지시키는 것으로 구성된다.Zy-crystal growth method of the present invention for achieving the above object is a rotation angle from the z-axis to the y-axis based on the x-axis after mounting the natural quartz raw material to the lower end of the autoclave (raw material dissolution) and the convection control plate After placing the plate-shaped seed crystal of 00 ° 00 '(0001) at the upper end (crystal growth part), the hydrothermal solution containing sodium hydroxide was added to the autoclave to fill and then sealed the autoclave, In the method of growing a zy-crystal for a quartz device using the deposition of Si element by convection while maintaining the temperature by lowering the temperature, raising the temperature of the lower part, and controlling the pressure, the hydrothermal solution further contains LiOH and NaNO 2 . And maintaining the temperature of the upper end at 350 ° C. or higher, and maintaining the internal pressure of the autoclave at 1800 bar or higher.

도 1은 통상적인 zy-크리스탈을 성장시키기 위한 오토클래이브의 측단면도이고,1 is a side cross-sectional view of an autoclave for growing conventional zy-crystals,

도 2는 종래의 방법에 따라 zy-크리스탈 성장시의 온도 조건을 나타낸 그래프이며,2 is a graph showing the temperature conditions during zy-crystal growth according to the conventional method,

도 3은 종래의 또 다른 방법에 따라 zy-크리스탈 성장시의 온도 조건을 나타낸 그래프이고,3 is a graph showing the temperature conditions during zy-crystal growth according to another conventional method,

도 4는 본 발명 및 종래의 방법에 따라 제조된 zy-크리스탈의 성장 단면을 나타낸 개략도이다.4 is a schematic view showing a growth cross section of zy-crystals prepared according to the present invention and conventional methods.

* 도면의 주요부분에 대한 부호의 설명 *Explanation of symbols on the main parts of the drawings

1: 천연(저순도)의 SiO2의 수정원료,1: modified raw material of natural (low purity) SiO 2 ,

2: 수열용액(solution for hydrothermal Method)2: solution for hydrothermal method

3: 대류조절판(baffle)3: convection baffle

4: 판상 종자결정(seed)4: seed seed

10: 오토클래이브(autoclave).10: autoclave.

이하 본 발명을 첨부된 도면을 참조하여 좀 더 구체적으로 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

도 1은 통상적인 zy-크리스탈을 성장시키기 위한 오토클래이브의 측단면도이다. 도 1에 도시된 바와 같이, zy-크리스탈은 SiO2와 같은 천연수정원료(1)를 오토클래이브(10)의 하단부에 투입하고 대류조절판(3)을 얹은 후 판상 종자결정(4)을 오토클래이브의 상단부에 위치시킨 후, 수산화나트륨을 포함하는 수열용액(2)을 오토크래이브에 투입하여 충진시킨 후 오토크래이브를 밀봉시킨 다음, 상단부 온도를 강하시키고 하단부 온도를 승온시키며 압력을 조절하여 일정기간동안 유지시켜 성장시킨다.1 is a side cross-sectional view of an autoclave for growing conventional zy-crystals. As shown in FIG. 1, zy-crystals inject a natural fertilizer 1 such as SiO 2 into the lower end of the autoclave 10, mount the convection control plate 3, and then automate the plate seed crystals 4. After placing it in the upper part of the clad, the hydrothermal solution (2) containing sodium hydroxide was added to the autoclave and filled, and then the autoclave was sealed, and then the upper end temperature was lowered and the lower end temperature was raised and pressured. Adjust to keep for a certain period of time to grow.

상기 천연수정원료는 고순도 인공 석영인 SiO2를 생산하기 위해 사용하는 천연(저순도)의 SiO2원료를 의미하는데, 상기 수정원료는 일정한 지름을 갖도록 입자크기를 선택하며, 본 발명에 있어서는 오토클래이브(10)에 300중량부 이상 투입하는데, 300중량부 미만으로 수정원료가 투입되면 원하는 두께만큼의 단결정을 얻지 못하는 문제가 있다.The natural modified raw material means a natural (low purity) SiO 2 raw material used to produce SiO 2 which is high purity artificial quartz, and the modified raw material selects a particle size to have a constant diameter, and in the present invention, the autoclave Although more than 300 parts by weight into the eve 10, if the raw material is less than 300 parts by weight there is a problem that can not be obtained a single crystal of the desired thickness.

또한, 상기 대류조절판(baffle; 3)은 오토클래이브의 상단과 하단의 대류현상을 원할하게 유지시킬 수 있도록 사용하는 원판이며, 상기 대류조절판은 통상적으로 2∼10%의 개공도를 갖는 것이 바람직한데, 상기 개공도가 2% 미만이거나 10%를 초과하면 대류현상이 원할하지 못하여 단결정을 육성하기 어려워진다.In addition, the convection control plate (baffle) (3) is a disc used to keep the convection phenomenon of the top and bottom of the autoclave smoothly, it is preferable that the convection control plate usually has a porosity of 2 to 10%. However, when the porosity is less than 2% or more than 10%, convection is not desired and it is difficult to grow single crystals.

한편, 단결정을 육성할 때, 원소가 증착될 수 있도록 사용되어지는 고순도의 단결정판인 판상 종자결정(4)은 x축 기준으로 z축에서 y축으로 회전각이 약 00°00"이며, 성장 단결정은 이 판상 종자결정의 성질과 동일한 성질을 갖게 된다.상기 판상 종자결정은 본원의 참고문헌으로 포함된 종래의 미국특허 제6,001,171호 및 5,714,005에 기재되어 있으며, 상기 회전각이 00°00"가 아니면 효율이 떨어지는 문제가 있다.On the other hand, when growing a single crystal, the plate-shaped seed crystal 4, which is a high-purity single crystal plate used to deposit an element, has a rotation angle of about 00 ° 00 "from the z axis to the y axis with respect to the x axis. The single crystal will have the same properties as the plate seed crystals. The plate seed crystals are described in US Pat. Nos. 6,001,171 and 5,714,005, incorporated herein by reference, wherein the rotation angle is 00 ° 00 ". Or there is a problem of poor efficiency.

본 발명에 따르면, 수열합성법으로 단결정을 육성 및 성장시킬 때 사용되는 용액인 수열용액(2)은 3∼4%의 수산화나트륨 용액을 사용하고, LiOH와 NaNO2를 첨가제로 사용한다. LiOH와 NaNO2의 첨가량은 전체 수열용액의 2중량% 이하로 혼합하여 사용할 수 있고, 이를 초과하면 불순물이 많이 발생할 뿐만 아니라 오토클래이브 내벽의 상태가 오염되는 단점이 있다. 만약 첨가제로 기타의 다른 화공 약품을 사용할 경우에는 zy-크리스탈 내부에 다량의 불순물(Inclusion)이 함유될 뿐 아니라, 1회의 성장이 끝난 후 오토클래이브의 내부에 미세불순물이 남게 되어서 다음 번 성장시에 좋지 않은 영향을 미치게 된다.According to the present invention, the hydrothermal solution (2), which is a solution used for growing and growing single crystals by hydrothermal synthesis, uses 3 to 4% sodium hydroxide solution and LiOH and NaNO 2 as additives. LiOH and NaNO 2 may be used in an amount of 2 wt% or less of the total hydrothermal solution. If the amount of LiOH and NaNO 2 is exceeded, a large amount of impurities may be generated. If other chemicals are used as an additive, not only does it contain a large amount of inclusions in the zy-crystal, but it also leaves fine impurities in the interior of the autoclave after the first growth. It will have a negative impact on.

또한, 상기 수열용액 및 천연수정원료를 투입할 때, 수열합성법으로 단결정을 육성할 수 있는 전기로인 오토크래이브(10)에 80% 내지 85%로 충진시킨 후 오토크래이브를 밀봉시키는데, 80% 미만일 경우와 85%를 초과할 경우에는 육성후 단결정의 경도에 문제를 초래하는 경우가 있다.In addition, when the hydrothermal solution and the natural crystal raw material are added, the autoclave 10, which is an electric furnace capable of growing a single crystal by hydrothermal synthesis, is filled with 80% to 85%, and then the autoclave is sealed. When less than 80% and more than 85% may cause problems in the hardness of the single crystal after growth.

본 발명에 따르면, 상기 오토클래이브 상단부 온도는 350℃ 이상으로 유지시키며, 하단부의 온도는 상단부 보다 10℃ 이상 높도록 승온시켜, 천연 수정 원료가 용해하고 기화되어 대류조절판을 통해 상승하여 판상 종자 결정(seed)에 증착됨으로써 zy-크리스탈이 육성 및 성장된다. 이때, 상기 상부의 온도가 350℃ 이상인이유는 앞에서도 언급했듯이 종래에 사용되는 350℃ 미만의 온도를 이용할 경우, zy-크리스탈의 성장속도를 떨어뜨리고 불필요한 영역의 성장을 촉진하여 생산효율을 상당히 낮추는 결과를 초래하며(도 4 참조), 또한 온도를 350℃ 미만으로 하면 zy-크리스탈의 특성중 가장 중요한 Q값의 특성을 맞추기 위해서 성장속도를 낮춰야 하기 때문에 고체 불순물이 많이 함유될 우려가 있기 때문이다.According to the present invention, the temperature of the upper end of the autoclave is maintained at 350 ° C. or higher, and the temperature of the lower end is raised to 10 ° C. or higher than the upper end, and the natural quartz raw material is dissolved and vaporized to rise through the convection control plate to determine plate seed. By depositing on the seed, the zy-crystals are grown and grown. At this time, the reason why the temperature of the upper portion is 350 ℃ or more, as mentioned above, when using a temperature below 350 ℃ used conventionally, the growth rate of the zy-crystals and to promote the growth of unnecessary areas to considerably lower the production efficiency This results in a result (see Fig. 4), and if the temperature is lower than 350 ° C., the growth rate must be lowered in order to match the most important Q value among the characteristics of the zy-crystal. .

또한, 본 발명에서는 상기 오토클래이브의 내부 압력을 1800bar 이상으로 유지시키면서 zy-크리스탈을 성장 및 육성시킨다. 이때, 상기 내부압력이 1800bar 이상인 이유는 종래에 사용되는 1500bar이하의 온도를 이용한 경우 zy-크리스탈의 내부에 미세 불순물이 함유될 가능성이 상당히 높기 때문이다.In the present invention, the zy-crystals are grown and grown while maintaining the internal pressure of the autoclave at 1800 bar or more. At this time, the reason why the internal pressure is 1800 bar or more is because the possibility of containing fine impurities in the interior of the zy-crystal when using a temperature of less than 1500 bar conventionally used.

이와 같이, 본 발명에 따라 성장된 zy-크리스탈은 제조상 발생할 수 잇는 결함들이 적게되고, 품질이 균일하며, 생산성에 관한 측면에서도 상당한 잇점들이 있다. 그리고 본 발명에 따른 석영 디바이스용 zy-크리스탈은 진동자, 공진자 뿐만 아니라 필터(Filter)용 등 여러 분야에 적용이 가능하다.As such, zy-crystals grown in accordance with the present invention have fewer manufacturing defects, are uniform in quality, and have significant advantages in terms of productivity. In addition, the zy-crystal for a quartz device according to the present invention can be applied to various fields such as a filter as well as a vibrator and a resonator.

이하 실시예 및 비교예를 통하여 본 발명을 좀 더 구체적으로 살펴보지만, 하기 예에 본 발명의 범주가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to the following Examples.

비교예 1Comparative Example 1

φ20∼30mm 일정한 입자크기의 천연 수정 원료 350Kg을 철망 바스켓에 넣어 내용적 500ℓ의 도 1에 도시된 바와 같은 오토클래이브의 하단부(원료용해부)에 장착하고 개공도 3%의 대류 조절판을 얹은 후 ⅹ축 기준으로 z축에서 y축으로 회전각 00°00′(0001)인 판상 종자결정(seed)을 상단부(결정육성부)에 장착하였다. 3.5%인 수산화나트륨 수용액 300Kg에 LiOH와 NaNO2를 각각 1kg씩 혼입하여 제조한 수열용액을 충진율 83%이상에 맞춰 채취한 후 오토클래이브에 충진하였다. 오토클래이브를 밀봉하고 상단부 340℃, 하단부 360℃ 로 승온한 후 약 30일간 유지하여 결정을 육성하여 석영 디바이스용 zy-크리스탈을 성장시켰다.After putting 350Kg of natural quartz raw material of φ20 ~ 30mm constant particle size into the wire mesh basket, it is mounted on the lower part (raw material melting part) of autoclave as shown in Fig. A plate seed crystal having a rotation angle of 00 ° 00 '(0001) from the z-axis to the y-axis relative to the X-axis was mounted on the upper end (crystal growing part). A hydrothermal solution prepared by mixing 1 kg of LiOH and NaNO 2 in 300 Kg of 3.5% sodium hydroxide aqueous solution was collected at 83% or more, and filled in an autoclave. The autoclave was sealed and heated to 340 ° C at the top and 360 ° C at the bottom and held for about 30 days to grow crystals to grow zy-crystals for quartz devices.

비교예 2Comparative Example 2

비교예 1에서 시약(LiOH와 NaNO2)을 혼입하지 않고 나머지 조건은 실시예 1과 동일하게 실시하였다.In Comparative Example 1, the remaining conditions were performed in the same manner as in Example 1 without mixing the reagents (LiOH and NaNO 2 ).

비교예 3Comparative Example 3

비교예 1에서 상단부 온도를 350℃로 하고 동일한 온도차를 하단부에 두고, 시약(LiOH와 NaNO2)을 혼입하지 않고 나머지 조건은 실시예 1과 동일하게 실시하였다.In Comparative Example 1, the upper end temperature was set at 350 ° C., and the same temperature difference was set at the lower end, and the remaining conditions were performed in the same manner as in Example 1 without mixing reagents (LiOH and NaNO 2 ).

실시예 1Example 1

비교예 1에서 상단부 온도를 350℃로 하고 동일한 온도차를 하단부에 두고 나머지 조건은 실시예 1과 동일하게 실시하였다.In Comparative Example 1, the upper end temperature was 350 ° C., and the same temperature difference was placed at the lower end, and the remaining conditions were performed in the same manner as in Example 1.

상기 비교예 및 실시예에 의해 제조된 zy-크리스탈의 Q-값, 고체 불순물 순위, 단결정 두께, 〈+X〉영역 생성비율 및 생선성 등을 측정하였고, 그 결과를 하기 표 1에 나타내었다.The Q-values, solid impurity ranks, single crystal thicknesses, <+ X> region formation ratios, and fish properties of the zy-crystals prepared by the Comparative Examples and Examples were measured, and the results are shown in Table 1 below.

항목별 결과Itemized Results Q-값Q-value 고체 분순물Solid impurities 단결정 두께Single crystal thickness 〈+X〉영역 생성비율〈+ X〉 area creation ratio 생산성productivity 비교예 1Comparative Example 1 C등급C grade I등급Class I 18.2mm18.2mm 35%35% 56%56% 비교예 2Comparative Example 2 C등급C grade II등급Class II 17.9mm17.9mm 32%32% 54%54% 비교예 3Comparative Example 3 C등급C grade I등급Class I 22.3mm22.3mm 24%24% 67%67% 실시예 1Example 1 B등급Class B Ia등급Class Ia 23.5mm23.5mm 21%21% 73%73%

※Q-값의 순위: Aa등급〉A등급〉B등급〉C등급〉D등급〉E등급※ Q-value ranking: Aa class> A class> B class> C class> D class> E class

※고체 불순물 순위: Ia등급〉Ib등급〉I등급〉II등급〉III등급※ Solid impurity ranking: Ia class> Ib class> I class> II class> III class

상기 검사는 IEC 표준규격과 동일하게 측정하였으며, 상기 결과로부터 알 수 있는 바와 같이 전체적으로 결함이 감소하고 생산효율이 향상된 것을 볼 수 있다.The inspection was measured in the same manner as the IEC standard, and as can be seen from the above results, it can be seen that the overall defect is reduced and the production efficiency is improved.

전술한 바와 같이, 본 발명에 따라 성장된 zy-크리스탈은 제조상 발생할 수 잇는 결함들이 적게되고, 품질이 균일하며, 생산성에 관한 측면에서도 상당한 잇점들이 있다. 그리고 본 발명에 따른 석영 디바이스용 zy-크리스탈은 진동자, 공진자 뿐만 아니라 필터(Filter)용 등 여러 분야에 적용이 가능하다.As mentioned above, zy-crystals grown in accordance with the present invention have fewer manufacturing defects, are uniform in quality, and have significant advantages in terms of productivity. In addition, the zy-crystal for a quartz device according to the present invention can be applied to various fields such as a filter as well as a vibrator and a resonator.

Claims (2)

천연 수정원료를 오토클래이브의 하단부(원료용해부)에 장착하고 대류조절판을 얹은 후 x축을 기준으로 z축에서 y축으로 회전각 00°00′(0001)인 판상 종자 결정을 상단부(결정 육성부)에 위치시킨 후, 수산화나트륨을 포함하는 수열용액을 상기 오토클래이브에 투입하여 충진시킨 후 오토클래이브를 밀봉시킨 다음, 상단부 온도를 강하시키고 하단부 온도를 승온시키며 압력을 조절하여 일정기간동안 유지시키면서 대류현상에 의한 Si원소의 증착을 이용한 석영 디바이스용 zy-크리스탈의 성장방법에 있어서,The natural crystal raw material is mounted on the lower part of the autoclave (raw material dissolution part), the convection control plate is placed, and the plate seed crystals with a rotation angle of 00 ° 00 '(0001) from the z axis to the y axis with respect to the x axis are mounted on the upper part (crystal growth). Part), the hydrothermal solution containing sodium hydroxide is added to the autoclave and filled, and then the autoclave is sealed, and then the temperature of the upper part is lowered, the temperature of the lower part is increased, and the pressure is adjusted for a certain period of time. In the zy-crystal growth method for quartz devices using the deposition of Si element by convection while maintaining 상기 수열용액이 LiOH 및 NaNO2를 더욱 포함하며, 상기 상단부의 온도를 350℃ 이상으로 유지시키고, 상기 오토클래이브의 내부압력을 1800bar 이상으로 유지시키는 것을 특징으로 하는 zy-크리스탈의 성장방법.The hydrothermal solution further comprises LiOH and NaNO 2 , the temperature of the upper end is maintained at 350 ℃ or more, and the internal pressure of the autoclave to maintain the internal pressure of more than 1800 bar zy-crystal growth method. 제1항에 있어서, 상기 LiOH 및 NaNO2의 첨가량이 상기 수열용액에 대하여 2중량% 이하로 첨가됨을 특징으로 하는 zy-크리스탈의 성장방법.The method for growing zy-crystals according to claim 1, wherein the amount of LiOH and NaNO 2 is added in an amount of 2 wt% or less based on the hydrothermal solution.
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CN115573025A (en) * 2022-09-09 2023-01-06 北京石晶光电科技股份有限公司 Method for growing artificial quartz crystal raw material for high-purity quartz sand with purity of more than 5N

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