JP2009196867A5 - - Google Patents
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- JP2009196867A5 JP2009196867A5 JP2008042277A JP2008042277A JP2009196867A5 JP 2009196867 A5 JP2009196867 A5 JP 2009196867A5 JP 2008042277 A JP2008042277 A JP 2008042277A JP 2008042277 A JP2008042277 A JP 2008042277A JP 2009196867 A5 JP2009196867 A5 JP 2009196867A5
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- 239000010409 thin film Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 34
- 239000000758 substrate Substances 0.000 description 18
- 229910003363 ZnMgO Inorganic materials 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 210000002381 Plasma Anatomy 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 125000004433 nitrogen atoms Chemical group N* 0.000 description 1
- 230000003287 optical Effects 0.000 description 1
- 125000004430 oxygen atoms Chemical group O* 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Description
以下、この発明によるMgaZn1-aO単結晶薄膜の作製方法を実施するための最良の形態を説明する。
〔実施形態の概要〕
まず、この発明によるMgaZn1-aO単結晶薄膜の作製方法の実施形態の概要を説明する。
以下に説明する実施の形態においては、ZnO薄膜の作製において実績のある、例えば特許第３９４５７８２号公報に記載されているようなプラズマアシスト付きの反応性蒸着法を用いる。
Hereinafter, the best mode for carrying out the method for producing a Mg a Zn 1-a O single crystal thin film according to the present invention will be described.
[Outline of Embodiment]
First, an outline of an embodiment of a method for producing a Mg a Zn 1-a O single crystal thin film according to the present invention will be described.
In the embodiment described below, a reactive deposition method with plasma assist as described in, for example, Japanese Patent No. 3945782, which has a track record in the production of a ZnO thin film, is used.
通常、ZnOバルク単結晶は抵抗率が１００Ω・cm以上であるが、ZnO単結晶育成の際にドナー不純物（Al、Fe、Gaの単独あるいはそれらの組み合わせ）を、１．０×１０１７／ｃｍ３以上ドーピングすることによって、結晶性に優れ移動度が高く、基板の抵抗率を０．５Ω・cm以下にすることが可能なため、導電性基板として使用可能である。
また、ZnO単結晶基板の代わりにMgbZn1-bO（ただし、０＜ｂ≦１）単結晶基板を用いることにより格子定数や熱膨張係数のずれも解消できるため、発生する歪みもさらに抑制することが可能であり、より好ましい。
Normally, the resistivity of a ZnO bulk single crystal is 100 Ω · cm or more, but donor impurities (single or a combination of Al, Fe, and Ga) are added at 1.0 × 10 17 / cm during the growth of a ZnO single crystal. By doping 3 or more, the crystallinity is excellent and the mobility is high, and the resistivity of the substrate can be 0.5 Ω · cm or less, so that it can be used as a conductive substrate.
In addition, by using a Mg b Zn 1-b O (where 0 <b ≦ 1) single crystal substrate instead of a ZnO single crystal substrate, the lattice constant and the coefficient of thermal expansion can be eliminated. It can be suppressed, and is more preferable.
基板にAl2O3単結晶基板を用いることもできるが、その場合には、MgaZn1-aO（ただし、０≦a≦1）とは格子定数が大きく異なり、熱膨張係数も異なる。そこで、結晶性の良好な成長層を得るため、Al2O3単結晶上にMgaZn1-aO（ただし、０≦a≦1）のバッファ層を設けるのが望ましい。また、ZnO単結晶基板を用いる場合でも、そのZnO単結晶上にMgaZn1-aOバッファ層を設けるとよい。 An Al 2 O 3 single crystal substrate can be used as the substrate, but in that case, the lattice constant is significantly different from that of Mg a Zn 1-a O (where 0 ≦ a ≦ 1), and the thermal expansion coefficient is also different. . Therefore, in order to obtain a growth layer with good crystallinity, it is desirable to provide a buffer layer of Mg a Zn 1-a O (where 0 ≦ a ≦ 1) on the Al 2 O 3 single crystal. Even when a ZnO single crystal substrate is used, an Mg a Zn 1-a O buffer layer is preferably provided on the ZnO single crystal.
その真空状態で基板加熱用ヒータ１によって基板２を成膜時の温度またはそれよりも高い温度に加熱して一定時間保持することによって、基板２の成膜面をサーマルクリーニングした後、基板２の加熱温度を成膜温度に調整する。その成膜温度は３００〜１０００℃の間とする。３００℃より低いと結晶性が著しく悪くなり、１０００℃を超えると成膜できなくなる。 In this vacuum state, the substrate 2 is heated to the temperature at the time of film formation by the substrate heating heater 1 or higher and held for a certain period of time to thermally clean the film formation surface of the substrate 2, The heating temperature is adjusted to the film formation temperature . The film forming temperature is between 300 and 1000 ° C. When the temperature is lower than 300 ° C., the crystallinity is remarkably deteriorated.
酸素と窒素は分圧にて窒素：酸素＝1：０．５〜５になるようにしてから、ルツボ６の上方のシャッタ５を開け、MgxZn1-x合金からなる蒸着材料を加熱して蒸発させ、高周波プラズマ雰囲気中に含まれる酸素及び窒素原子と基板２上で結合させ、窒素ドープのｐ形MgaZn1-aO（ただし、０≦ａ≦１）薄膜を成長させて成膜する。
酸素と窒素の分圧比を上記の範囲にする理由は、窒素の割合がこれより大きくなると結晶性が悪くなり、逆に小さいとキャリア濃度が低くなってｐ形層の抵抗が高くなってしまうためである。成膜時間は３０〜１８０分の間とし、膜厚は０．２〜１．０μｍとする。成膜時間はこの膜厚を得るために必要な時間である。
Oxygen and nitrogen are made to have a partial pressure of nitrogen: oxygen = 1: 0.5 to 5, and then the shutter 5 above the crucible 6 is opened and the vapor deposition material made of Mg x Zn 1-x alloy is heated. This is evaporated and bonded to oxygen and nitrogen atoms contained in the high-frequency plasma atmosphere on the substrate 2 to grow a nitrogen-doped p-type Mg a Zn 1-a O (where 0 ≦ a ≦ 1) thin film. Film.
The reason why the partial pressure ratio of oxygen and nitrogen is within the above range is that the crystallinity is deteriorated when the ratio of nitrogen is larger than this, and conversely, the carrier concentration is lowered and the resistance of the p-type layer is increased. It is. The film formation time is 30 to 180 minutes, and the film thickness is 0.2 to 1.0 μm. The film formation time is the time necessary to obtain this film thickness.
〔作製したMgZnO膜の評価〕
上記の条件で成膜したMgaZn1-aO（ただし、０≦ａ≦１）膜（以下、「ZnMgO薄膜」という）の評価を行った。
図２は、この発明によってZnO単結晶基板上に成膜したZnMgO薄膜のX線回折（ＸＲＤ）逆格子空間マップの測定結果を示す。その測定にはPhilips社製の薄膜材料結晶性解析Ｘ線回折装置であるX’ pert ＭＲＤを使用した。
[Evaluation of prepared MgZnO film]
The Mg a Zn 1-a O (where 0 ≦ a ≦ 1) film (hereinafter referred to as “ ZnMgO thin film ”) formed under the above conditions was evaluated.
FIG. 2 shows a measurement result of an X-ray diffraction (XRD) reciprocal lattice space map of a ZnMgO thin film formed on a ZnO single crystal substrate according to the present invention. For this measurement, X 'pert MRD, which is an X-ray diffraction apparatus for crystallinity analysis of a thin film material manufactured by Philips, was used.
この図２から分るように、基板であるZnOの（０００２）面のピークＰ１と作製した薄膜であるZnMgOの（０００２）面のピークＰ２が観察されている。スポットが扁平に伸びているのは装置の光学系の広がりのためである。ZnMgOの薄膜において他の配向面は観察されず、エピタキシャル成長しており、基板のZnO単結晶よりもわずかに広いピークとはなっているものの鋭いピークであり、結晶性は良好である。また、ZnO中にMgが取り込まれることにより、ｃ軸長が小さくなっていることが分る。これより、取り込まれたMgはZnと置換し、六方晶のZnMgO混晶が形成されていることと考えられる。
図２において、平行四辺形の枠内が測定範囲を示しており、曲線はその測定結果を示している。また、横軸のＱｘ、縦軸のはＱｙは逆格子単位（reciprocal lattice unit）×１０４〔rlu〕を示している。
As can be seen from FIG. 2, a peak P1 on the (0002) plane of ZnO as a substrate and a peak P2 on the (0002) plane of ZnMgO as a fabricated thin film are observed. The spots are flat because of the spread of the optical system of the apparatus. No other orientation plane was observed in the ZnMgO thin film, and it was epitaxially grown. Although it is a slightly broader peak than the ZnO single crystal of the substrate, it is a sharp peak and the crystallinity is good. It can also be seen that the c-axis length is reduced by the incorporation of Mg into ZnO. From this, it is considered that the incorporated Mg is substituted with Zn, and a hexagonal ZnMgO mixed crystal is formed.
In FIG. 2, the inside of the parallelogram frame indicates the measurement range, and the curve indicates the measurement result. Further, Qx on the horizontal axis and Qy on the vertical axis indicate reciprocal lattice units × 10 4 [rlu].
図３は、ZnO単結晶基板上に作製したZnMgO薄膜のX線回折（ＸＲＤ）における2θ−ωスキャンの結果である。横軸は2θ（deg.）であり、縦軸はX線回折強度（Intensity）（a.u.）である。a.u.は任意単位でありX線回折強度の相対的な強度を示す。34.42
(deg.) のピークＰ１は基板であるZnOの （０００２）面 のピークであり、34.46 (deg.) のピークＰ２は作製したZnMgOの薄膜のピークである。
FIG. 3 shows the results of 2θ-ω scanning in X-ray diffraction (XRD) of a ZnMgO thin film formed on a ZnO single crystal substrate. The horizontal axis is 2θ (deg.), And the vertical axis is X-ray diffraction intensity (Intensity) (au). au is an arbitrary unit and indicates the relative intensity of the X-ray diffraction intensity. 34.42
The peak P1 of (deg.) is the (0002) plane peak of ZnO as the substrate, and the peak P2 of 34.46 (deg.) is the peak of the produced ZnMgO thin film.
図５は、ZnO単結晶とZnO単結晶基板上に作製したZnMgO薄膜の反射スペクトルを示す線図であり、横軸は光子エネルギー（Photon
energy）（eV）、縦軸は反射率Ｒ（％）である。この図５において、破線で示すZnO単結晶では光子エネルギーの約３．３ eVにバンド端の吸収が見られる。それに対して、実線で示すZnMgO薄膜においては基板であるZnO単結晶のバンド端の吸収とZnMgO薄膜のバンド端の吸収がそれぞれ光子エネルギーの約３．３
eVと３．３７ eVに観察される。これより、ZnO中に取り込まれたMgはZnと置換し、六方晶のZnMgO混晶が形成されてバンドギャップが約70 meV大きくなっていると考えられる。
FIG. 5 is a diagram showing the reflection spectrum of a ZnMgO thin film fabricated on a ZnO single crystal and a ZnO single crystal substrate, and the horizontal axis represents photon energy (Photon energy).
energy) (eV), and the vertical axis represents the reflectance R (%) . In FIG. 5, in the ZnO single crystal shown by a broken line, absorption at the band edge is observed at a photon energy of about 3.3 eV. On the other hand, in the ZnMgO thin film indicated by the solid line, the absorption at the band edge of the ZnO single crystal as the substrate and the absorption at the band edge of the ZnMgO thin film are about 3.3 photon energy, respectively.
Observed at eV and 3.37 eV. From this, it is considered that Mg taken into ZnO is substituted for Zn, and a hexagonal ZnMgO mixed crystal is formed, and the band gap is increased by about 70 meV.
この発明は、高品質でMg濃度を容易に制御できる量産性に優れたMgaZn1-aO（ただし、０≦ａ≦１）の単結晶薄膜の作製方法を提供する。この作製方法により作製できるMgaZn1-aO（ただし、０≦ａ≦１）の単結晶薄膜は発光ダイオードや半導体レーザ素子、及びそれを利用する各種表示装置やプリンタなど、紫外線を発生したりそれを使用する装置等の広範な用途に利用可能である。また、紫外線センサなどの受光素子としても利用可能である。 The present invention provides a method for producing a single-crystal thin film of Mg a Zn 1-a O (provided that 0 ≦ a ≦ 1), which has high quality and can easily control the Mg concentration and has excellent mass productivity. The Mg a Zn 1-a O (0 ≦ a ≦ 1) single crystal thin film that can be produced by this production method generates ultraviolet rays such as light emitting diodes, semiconductor laser elements, and various display devices and printers using the same. It can be used for a wide range of applications such as a device using the same. It can also be used as a light receiving element such as an ultraviolet sensor.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2008042277A JP5019326B2 (en) | 2008-02-23 | 2008-02-23 | Method for producing MgaZn1-aO single crystal thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2008042277A JP5019326B2 (en) | 2008-02-23 | 2008-02-23 | Method for producing MgaZn1-aO single crystal thin film |
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| Publication Number | Publication Date |
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| JP2009196867A JP2009196867A (en) | 2009-09-03 |
| JP2009196867A5 true JP2009196867A5 (en) | 2011-03-17 |
| JP5019326B2 JP5019326B2 (en) | 2012-09-05 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101213133B1 (en) * | 2010-02-19 | 2012-12-18 | 전남대학교산학협력단 | ZnMgAlO thin films of UV ragne single crystalline Lattice matched to ZnO and Method for manufacturing the same |
| KR20140128157A (en) * | 2013-04-26 | 2014-11-05 | 오씨아이 주식회사 | Method for growing single crystal using plasma |
| PL238652B1 (en) * | 2017-11-28 | 2021-09-20 | Inst Fizyki Polskiej Akademii Nauk | Method for producing structures with the three-component layers of Zn₁-ₓMgₓO |
| CN109301036A (en) * | 2018-11-14 | 2019-02-01 | 长春理工大学 | A kind of uniform MgZnO film technology of preparing based on laser sintered method |
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| JP4540201B2 (en) * | 2000-09-13 | 2010-09-08 | 独立行政法人産業技術総合研究所 | Method for manufacturing semiconductor device having ZnO-based oxide semiconductor layer |
| JP2004207441A (en) * | 2002-12-25 | 2004-07-22 | Sharp Corp | Oxide semiconductor light-emitting device |
| JP2004304166A (en) * | 2003-03-14 | 2004-10-28 | Rohm Co Ltd | ZnO SEMICONDUCTOR DEVICE |
| JP3945782B2 (en) * | 2005-09-06 | 2007-07-18 | シチズン東北株式会社 | Semiconductor light emitting device and manufacturing method thereof |
| JP5122738B2 (en) * | 2005-11-01 | 2013-01-16 | スタンレー電気株式会社 | Method for manufacturing ZnO crystal or ZnO-based semiconductor compound crystal, and method for manufacturing ZnO-based light emitting device |
| JP4939844B2 (en) * | 2006-06-08 | 2012-05-30 | ローム株式会社 | ZnO-based semiconductor device |
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