JP4427347B2 - Method for producing ZnO single crystal - Google Patents
Method for producing ZnO single crystal Download PDFInfo
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- JP4427347B2 JP4427347B2 JP2004038778A JP2004038778A JP4427347B2 JP 4427347 B2 JP4427347 B2 JP 4427347B2 JP 2004038778 A JP2004038778 A JP 2004038778A JP 2004038778 A JP2004038778 A JP 2004038778A JP 4427347 B2 JP4427347 B2 JP 4427347B2
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Description
本発明は、トランジスタ、ダイオード、センサ、発振器など広範囲なデバイスの作製に用いられる酸化亜鉛（ＺｎＯ）単結晶の製造方法に関するものである。 The present invention relates to a method for manufacturing a zinc oxide (ZnO) single crystal used for manufacturing a wide range of devices such as transistors, diodes, sensors, and oscillators.
酸化亜鉛（ＺｎＯ、以下、「ＺｎＯ」という。）の単結晶化に関しては、非特許文献１が報告されている。この非特許文献１には水熱法によるＺｎＯ単結晶の育成が記載されている。
この育成法によれば、ＺｎＯ焼結体を結晶育成装置内の下部に置き、一方、ＺｎＯ種結晶を当該育成装置の上部にそれぞれ配置し、次いで水酸化カリウム（ＫＯＨ）及び水酸化リチウム（ＬｉＯＨ）から成るアルカリ水溶液の溶媒（以下、「アルカリ溶媒」という。）を充填する。
この状態で、結晶育成装置内を３７０〜４００°Ｃの育成温度、７００〜１０００ｋｇ／ｃｍ2 の圧力で、また、育成装置内の上部の温度が下部の温度より１０〜１５°Ｃ低くして運転することによりＺｎＯ単結晶を育成している。
Non-Patent Document 1 has been reported regarding single crystallization of zinc oxide (ZnO, hereinafter referred to as “ZnO”). This non-patent document 1 describes the growth of ZnO single crystals by a hydrothermal method.
According to this growth method, the ZnO sintered body is placed in the lower part of the crystal growth apparatus, while the ZnO seed crystals are respectively arranged in the upper part of the growth apparatus, and then potassium hydroxide (KOH) and lithium hydroxide (LiOH). ) In an aqueous alkaline solution (hereinafter referred to as “alkaline solvent”).
In this state, the inside of the crystal growth apparatus is set to a growth temperature of 370 to 400 ° C. and a pressure of 700 to 1000 kg / cm 2 , and the temperature in the upper part of the growth apparatus is set to 10 to 15 ° C. lower than the temperature of the lower part. A ZnO single crystal is grown by operation.
上記のように育成溶液としてアルカリ溶媒のみを用いた場合には育成環境が還元性雰囲気になり、酸素欠陥が多く存在し、電気抵抗率は１〜１０2Ωｃｍとなる。そこで育成環境を酸素雰囲気にするために過酸化水素（Ｈ2Ｏ2）を添加し、１０8〜１０10Ωｃｍを得ている。 When only an alkaline solvent is used as the growth solution as described above, the growth environment is a reducing atmosphere, there are many oxygen defects, and the electrical resistivity is 1 to 10 2 Ωcm. Therefore, hydrogen peroxide (H 2 O 2 ) is added to make the growth environment in an oxygen atmosphere, and 10 8 to 10 10 Ωcm is obtained.
さらに、特許文献１には、図３に示すように、内径３０ｍｍ×高さ３００ｍｍのほぼ円柱形状をなし、内容積は２５０ｍｌである育成容器１１０は、熱電対挿入部１１２、１１２’、開孔率５％のバッフル板１０３、原料充填部１１４、結晶育成部１１６、ＺｎＯ種結晶１０７をＰｔ線１０９を貫通させて吊り下げたＰｔフレーム１０５から構成され、該育成容器１１０にアルカリ溶媒に加えて、過酸化水素（Ｈ2Ｏ2）及び水酸化アンモニウム（ＮＨ4ＯＨ）を添加することにより電気抵抗率１０6〜１０11ΩｃｍのＺｎＯ単結晶を得ている。特許文献１に、アンモニウムイオン（ＮＨ4 +） は、Ｌｉイオンと異なり結晶中には混入しないため抵抗率のバラツキを抑制する効果があるとしている。
Further, in Patent Document 1, as shown in FIG. 3, the growth container 110 having a substantially cylindrical shape with an inner diameter of 30 mm × height of 300 mm and an internal volume of 250 ml is provided with thermocouple insertion portions 112 and 112 ′, open holes. A baffle plate 103 having a rate of 5%, a raw material filling unit 114, a crystal growth unit 116, and a Pt frame 105 in which a ZnO seed crystal 107 is suspended through a
しかしながら、特許文献１に記載の製造法は、酸素欠陥の数を減少させるために酸素を多量に供給しようとするものであり、更なる自由電子密度を減少させ、高抵抗化を図ること及び、Ｐ型伝導性をもった結晶を製造することはできないものである。 However, the manufacturing method described in Patent Document 1 is intended to supply a large amount of oxygen in order to reduce the number of oxygen defects, to further reduce the free electron density and increase resistance, Crystals with P-type conductivity cannot be produced.
本発明は、上記のような従来技術の課題等に鑑みてなされたものであり、その目的とするところは、半絶縁性基板更にＰ型半導体基板を供するＺｎＯ単結晶の製造方法を提供することにある。上記多量に存在すると思われる酸素欠陥の位置に窒素原子を配位しようとするものである。 The present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide a method of manufacturing a ZnO single crystal that provides a semi-insulating substrate and a P-type semiconductor substrate. It is in. It is intended to coordinate a nitrogen atom at the position of the oxygen defect that is considered to exist in a large amount.
本発明は、上記目的を達成するために、亜硝酸イオンを用いることにより多量に存在する酸素欠陥の位置に窒素原子を配位して、ＺｎＯを主成分とする単結晶から半絶縁性基板及びＰ型半導体基板を供することが可能な結晶の製造方法を特徴とする。 In order to achieve the above-mentioned object, the present invention uses a nitrite ion to coordinate a nitrogen atom at a position of a large amount of oxygen defects, from a single crystal mainly composed of ZnO to a semi-insulating substrate, and It is characterized by a crystal manufacturing method capable of providing a P-type semiconductor substrate.
本発明の結晶の製造方法は、酸化亜鉛（ＺｎＯ）焼結体原料を容器下部の原料充填部に、ＺｎＯ種結晶を容器上部の結晶育成部にそれぞれ配置するとともに、亜硝酸イオン（ＮＯ2 +）を含有するアルカリ溶媒（ミネラライザー）を容器に充填し、原料充填部の温度が結晶育成部の温度より高くなるように容器内温度を制御して水熱条件下でＺｎＯ単結晶を育成する製造方法である。 The method for producing a crystal of the present invention comprises disposing a zinc oxide (ZnO) sintered body raw material in a raw material filling portion at the bottom of the container and a ZnO seed crystal in a crystal growing portion at the top of the container, and nitrite ions (NO 2 + ) Containing an alkaline solvent (mineralizer), and the ZnO single crystal is grown under hydrothermal conditions by controlling the temperature in the container so that the temperature of the raw material filling part is higher than the temperature of the crystal growing part. It is a manufacturing method.
以上の説明からわかるように、本発明の結晶製造方法によれば、ミネラライザーに亜硝酸イオンを生ずるミネラライザーを加えることにより得られた結晶に効率よく窒素がドーピングされ、アクセプターとして機能し、幅広い抵抗率制御が可能となり、薄膜トランジスタや圧電振動子などのデバイスを形成するために必要な半絶縁性基板を提供することができる。また本発明によればＰＮ接合を有するデバイスの作製に有用なＰ型結晶基板を提供することができる。 As can be seen from the above description, according to the crystal manufacturing method of the present invention, the crystal obtained by adding a mineralizer that generates nitrite ions to the mineralizer is efficiently doped with nitrogen, functions as an acceptor, and has a wide range. The resistivity can be controlled, and a semi-insulating substrate necessary for forming a device such as a thin film transistor or a piezoelectric vibrator can be provided. In addition, according to the present invention, a P-type crystal substrate useful for manufacturing a device having a PN junction can be provided.
以下本発明の実施例について説明する。本発明は、これら実施例に限定されるものではない。
図１は、ＺｎＯ単結晶を育成するための育成容器及びその内筒容器を示す概略図である。
本発明で使用される育成容器は、図３で示されたものと同様に、溶媒１０で満たされたライナー８内に、白金ラック７を図２に示すように挿入して、ＺｎＯの種結晶の育成が行われる。
白金ラック７には、ＺｎＯ原料１のための原料充填容器２、バッフル板３、種結晶５を白金線６で止着させた種結晶保持棒４が具備されている。
Examples of the present invention will be described below. The present invention is not limited to these examples.
FIG. 1 is a schematic view showing a growth container for growing a ZnO single crystal and an inner cylinder container thereof.
In the same manner as shown in FIG. 3, the growth container used in the present invention is inserted into the liner 8 filled with the solvent 10 with the platinum rack 7 as shown in FIG. Is trained.
The platinum rack 7 includes a raw material filling container 2 for the ZnO raw material 1, a baffle plate 3, and a seed crystal holding rod 4 in which a seed crystal 5 is fixed by a platinum wire 6.
本発明のＺｎＯ単結晶を育成する製造方法の実施例を以下に説明する。
まず、高純度ＺｎＯ粉末をプレス機で圧縮成形し、該圧縮成型されたＺｎＯを、１，０００°Ｃ以上で１時間以上焼結した焼結体を図１に示す白金で作られたラック７の原料充填部２に充填する。
上記のＺｎＯ焼結体原料１を原料充填容器２に入れ、種結晶保持棒４にＺｎＯ種結晶５を白金線６で吊って固定することによって止着される。
Examples of the production method for growing the ZnO single crystal of the present invention will be described below.
First, a rack 7 made of platinum shown in FIG. 1 is a sintered body obtained by compression-molding high-purity ZnO powder with a press and sintering the compression-molded ZnO at 1,000 ° C. or more for 1 hour or more. The raw material filling part 2 is filled.
The above-described ZnO sintered body raw material 1 is put in the raw material filling container 2, and the ZnO seed crystal 5 is suspended and fixed to the seed crystal holding rod 4 by a platinum wire 6.
次いで、白金ラック７は、白金ライナー８に挿入され、次に、白金ライナー８に水酸化カリウム（ＫＯＨ）を３モル／Ｌ、水酸化リチウム（ＬｉＯＨ）を１モル／Ｌ、ＫＮＯ2を０．０１〜１．５モル／Ｌからなるミネラライザー１０を注入する。ミネラライザーの量は育成温度、圧力により適量注入する。 Next, the platinum rack 7 is inserted into the platinum liner 8. Next, the platinum liner 8 is filled with 3 mol / L of potassium hydroxide (KOH), 1 mol / L of lithium hydroxide (LiOH), and 0.02 of KNO 2 . A mineralizer 10 consisting of 01 to 1.5 mol / L is injected. An appropriate amount of mineralizer is injected depending on the growth temperature and pressure.
次にライナーキャップ９で蓋をされ溶接される。溶接された育成容器はオートクレーブ１１中に設置される。このライナー８とオートクレーブ１１との間には圧力の調整を行うために純水１２を注入する、純水の量は温度、圧力により適量を注入する。オートクレーブの周囲にはヒータ１３が取り付けられ、これによりオートクレーブを加熱する。 温度３００〜６００°Ｃ、圧力５００〜１２００気圧で水熱合成を実施した。原料充填部の温度と結晶育成部の温度の差は１５°Ｃから４０°Ｃで育成を行った。 Next, the liner cap 9 is covered and welded. The welded growth vessel is installed in the autoclave 11. Pure water 12 is injected between the liner 8 and the autoclave 11 to adjust the pressure. An appropriate amount of pure water is injected according to temperature and pressure. A heater 13 is attached around the autoclave to heat the autoclave. Hydrothermal synthesis was performed at a temperature of 300 to 600 ° C. and a pressure of 500 to 1200 atmospheres. The difference between the temperature of the raw material filling portion and the temperature of the crystal growth portion was grown at 15 ° C. to 40 ° C.
育成されたＺｎＯ単結晶に含まれる元素について、ＳＩＭＳ分析を行ったところ最高１０18／ｃｍ3の窒素がドープされていることがわかった。また、電気的測定からＰ型伝導性を確認することができた。
アルカリ溶媒として水酸化カリウム（ＫＯＨ）、水酸化リチウム（ＬｉＯＨ）の代わりにＮａＯＨ、Ｌｉ2ＣＯ3などであっても本発明は適用できる。
When the element contained in the grown ZnO single crystal was subjected to SIMS analysis, it was found that a maximum of 10 18 / cm 3 nitrogen was doped. Moreover, P-type conductivity could be confirmed from electrical measurements.
The present invention can be applied even if potassium hydroxide (KOH) or lithium hydroxide (LiOH) is used as the alkaline solvent instead of NaOH, Li 2 CO 3 or the like.
上記ミネラライザーＫＮＯ2の代わりにＬｉＮＯ2、ＮａＮＯ2などの亜硝酸イオンをもつミネラライザーであっても本発明は有効である。
The present invention is effective even for a mineralizer having nitrite ions such as LiNO 2 and NaNO 2 instead of the above-described mineralizer KNO 2 .
１ 原料
２ 原料充填容器
３ バッフル版
４ 種結晶保持棒
５ 種結晶
６ 白金線
７ ラック
８ ライナー
９ ライナーキャップ
１０ 溶媒
１１ オートクレーブ
１２ 純水
１３ ヒータ
DESCRIPTION OF SYMBOLS 1 Raw material 2 Raw material filling container 3 Baffle plate 4 Seed crystal holding rod 5 Seed crystal 6 Platinum wire 7 Rack 8 Liner 9 Liner cap 10 Solvent 11 Autoclave 12 Pure water 13 Heater
Claims (1)
を特徴とするＺｎＯ単結晶の製造方法。 The ZnO sintered body material is placed in the raw material filling part at the bottom of the container, the ZnO seed crystal is placed in the crystal growth part at the top of the container, and a mineralizer containing nitrite ions (NO 2 + ) is filled in the container, A method for producing a ZnO single crystal, comprising growing the ZnO single crystal under hydrothermal conditions by controlling the temperature in the container so that the temperature of the filling portion is higher than the temperature of the crystal growth portion.
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| JP4427347B2 true JP4427347B2 (en) | 2010-03-03 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10156024B2 (en) | 2013-05-31 | 2018-12-18 | Ngk Insulators, Ltd. | Zinc oxide free-standing substrate and method for manufacturing same |
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| JP5276769B2 (en) * | 2004-10-01 | 2013-08-28 | 東京電波株式会社 | Hexagonal wurtzite single crystal, method for producing the same, and hexagonal wurtzite single crystal substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10156024B2 (en) | 2013-05-31 | 2018-12-18 | Ngk Insulators, Ltd. | Zinc oxide free-standing substrate and method for manufacturing same |
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