JP3465345B2 - Boron-containing aluminum nitride thin film and manufacturing method - Google Patents
Boron-containing aluminum nitride thin film and manufacturing methodInfo
- Publication number
- JP3465345B2 JP3465345B2 JP11652494A JP11652494A JP3465345B2 JP 3465345 B2 JP3465345 B2 JP 3465345B2 JP 11652494 A JP11652494 A JP 11652494A JP 11652494 A JP11652494 A JP 11652494A JP 3465345 B2 JP3465345 B2 JP 3465345B2
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- JP
- Japan
- Prior art keywords
- boron
- thin film
- aluminum nitride
- containing aluminum
- nitride thin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Crystals, And After-Treatments Of Crystals (AREA)
- Chemical Vapour Deposition (AREA)
Description
【０００１】[0001]
【産業上の利用分野】工具，耐摩部品，表面弾性波素
子，発光素子，高熱伝導ヒートシンクなどに用いられる
硼素含有窒化アルミニウム薄膜。[Industrial application] Boron-containing aluminum nitride thin films used for tools, wear resistant parts, surface acoustic wave devices, light emitting devices, high heat conduction heat sinks, etc.
【０００２】[0002]
【従来の技術】窒化ホウ素や窒化アルミニウムなどの高
い硬度を有する窒化物は天然には存在せず粉体や薄膜の
合成が試みられてきた。窒化アルミニウムはウルツ鉱型
の結晶構造をもち、高い硬度、速い音速、広いバンドギ
ャップを有し、粉体とその焼結体および薄膜が製造され
ている。大型単結晶が製造できないために配向性の薄膜
または薄膜として工具、高周波用表面弾性波フィルタ
ー、短波長発光素子などとして実用化あるいは開発研究
が進められてきた。2. Description of the Related Art Nitride having a high hardness such as boron nitride and aluminum nitride does not exist in nature, and attempts have been made to synthesize powders and thin films. Aluminum nitride has a wurtzite type crystal structure, high hardness, fast sound velocity, and wide band gap, and powder, its sintered body, and a thin film are manufactured. Since large single crystals cannot be manufactured, practical thin films or thin films with orientation have been put into practical use or development research as tools, high frequency surface acoustic wave filters, short wavelength light emitting devices and the like.
【０００３】窒化ホウ素は窒素とホウ素がｓｐ２型混成
軌道で結合した六方晶型を代表とする低圧相と、窒素と
ホウ素がｓｐ３型混成軌道で結合した立方晶型またはウ
ルツ鉱型の結晶構造を有する高圧相とがあるが、高圧相
窒化ホウ素は良質な結晶としてはこれまで微細な粒子が
静的高圧法や爆縮法で合成されてきたのみであった。こ
のような高圧相窒化ホウ素の薄膜を高圧発生装置を用い
ずに合成する試みがこれまで多数成されてきたが、半導
体や高周波フィルターに必要とされる高い結晶性を持つ
高圧相窒化ホウ素膜は得られていない。Boron nitride has a low-pressure phase typified by a hexagonal type in which nitrogen and boron are bonded in an sp2 hybrid orbital, and a cubic or wurtzite type crystal structure in which nitrogen and boron are bonded in an sp3 hybrid orbital. The high-pressure phase boron nitride has a high-pressure phase, but fine particles of high-pressure phase boron nitride have heretofore been synthesized only by a static high-pressure method or an implosion method. Many attempts have been made to synthesize such a thin film of high-pressure phase boron nitride without using a high-pressure generator, but a high-pressure phase boron nitride film with high crystallinity required for semiconductors and high-frequency filters has been developed. Not obtained.
【０００４】特開平１−２３２６９５号公報には、薄膜
ＥＬ素子の誘電体層としてＡｌＮとＢＮからなるコンポ
ジット薄膜を用いることによって、位相が異なる交流パ
ルスや、正、逆方向の振幅が異なる交流パルスで駆動し
ても、長時間に渡り安定したＢ／Ｖ特性を持つ薄膜素子
が記載されている。しかしながらコンポジットがどのよ
うな結晶構造を有しているかについては記載がない。Japanese Unexamined Patent Publication No. 1-232695 discloses an AC pulse having different phases and an AC pulse having different amplitudes in the positive and reverse directions by using a composite thin film made of AlN and BN as a dielectric layer of a thin film EL element. It describes a thin film element having stable B / V characteristics for a long time even when driven by. However, there is no description about what kind of crystal structure the composite has.
【０００５】[0005]
【発明が解決しようとする課題】本願発明は、前記した
問題点を解決するために窒化アルミニウムよりも高い硬
度、広いバンドギャップ、大きな音速、を有し価電子制
御が容易で、結晶性のよいホウ素含有窒化アルミニウム
薄膜を提供することを目的とするものである。In order to solve the above-mentioned problems, the present invention has a higher hardness, a wider bandgap, and a higher sound velocity than aluminum nitride, is easy to control valence electrons, and has good crystallinity. It is intended to provide a boron-containing aluminum nitride thin film.
【０００６】[0006]
【課題を解決するための手段】発明者等はホウ素を含有
する窒化アルミニウム薄膜が、ウルツ鉱型窒化ホウ素お
よびウルツ鉱型窒化アルミニウムと同じ結晶構造を有
し、窒化アルミニウムよりも硬度、音速、バンドギャッ
プなどの点で優れ、ウルツ鉱型窒化ホウ素よりも高品質
の結晶性を持つ薄膜が容易に合成できる事に着目し、検
討および実験の結果以下の結論を得た。ホウ素、アルミ
ニウム、窒素からなり、ＢｘＡｌ１−ｘＮｙ（０．００
１≦ｘ≦０．７、０．８５≦ｙ≦１．０５）なる組成
と、ウルツ鉱型の結晶構造を有する３元系薄膜が、その
結晶性を高品質に保つように形成されたならば、窒化ア
ルミニウム薄膜より高い硬度、速い音速、広いバンドギ
ャップを有する高い機能性を示し、高圧相窒化硼素薄膜
よりもＸ線回折のロッキングカーブの半価幅が狭く、結
晶性および結晶の配向性が優れた高品質な結晶性をもつ
薄膜を提供するものである。このとき、用途にもよるが
厚さが１０ｎｍ以上３０μｍ以下であると工具、耐摩部
品、表面弾性波素子、発光素子、高熱伝導ヒートシンク
として利用する上で適している。基材としては、ダイヤ
モンド単結晶を用いることによって高配向性または単結
晶の硼素含有窒化アルミニウム薄膜を得ることができ
る。The inventors of the present invention have found that an aluminum nitride thin film containing boron has the same crystal structure as wurtzite type boron nitride and wurtzite type aluminum nitride, and has a hardness, a sound velocity and a band higher than those of aluminum nitride. Focusing on the fact that a thin film having excellent crystallinity and higher quality than wurtzite boron nitride, which is excellent in terms of gaps, etc., can be easily synthesized, the following conclusions were obtained as a result of examinations and experiments. Boron, aluminum, consists of nitrogen, B x Al 1-x N y (0.00
1 ≦ x ≦ 0.7, 0.85 ≦ y ≦ 1.05) and a ternary thin film having a wurtzite crystal structure, if it is formed so as to maintain its crystallinity at high quality. For example, it exhibits higher hardness, higher sonic velocity, and wider bandgap than aluminum nitride thin film, narrower half-width of rocking curve of X-ray diffraction than high-pressure phase boron nitride thin film, and crystallinity and crystal orientation. Provides a thin film having excellent high quality crystallinity. At this time, when it depends The thickness on the application is a 10 n m above 30μm or less tools, wear parts, surface acoustic wave devices, light - emitting element is suitable in using as high thermal conductivity heat sink. As the base material, diamond
By using the Mondo single crystal , a highly oriented or single crystal boron-containing aluminum nitride thin film can be obtained.
【０００７】更にこのようなホウ素含有窒化アルミニウ
ム薄膜を作成するには、アルミニウム、ホウ素、窒化ア
ルミニウム、窒化ホウ素、アルミニウム−ホウ素合金の
中から選ばれた材料をターゲットとして、すくなくとも
窒素またはアンモニアを含むガス雰囲気でスパッタ法に
よって硼素含有窒化アルミニウム薄膜を形成するか、ま
たはすくなくともホウ素およびアルミニウムを含有する
ハロゲン化物または水素化物または有機金属化合物、金
属アルコキシドを水素または不活性ガスで希釈して原料
として供給しプラズマＣＶＤ法によって硼素含有窒化ア
ルミニウム薄膜を形成する方法が好ましいことを見いだ
した。上記の製造方法でダイヤモンド単結晶上にホウ素
含有窒化アルミニウム薄膜が適当な条件で形成された場
合には、高配向性または単結晶のホウ素含有窒化アルミ
ニウム薄膜をえることができる。このようにして得られ
たホウ素含有窒化アルミニウムは、基板上に析出させた
ままでも、また必要によっては基板を除去して使用する
ことができる。Further, in order to form such a boron-containing aluminum nitride thin film, a gas containing at least nitrogen or ammonia is targeted by using a material selected from aluminum, boron, aluminum nitride, boron nitride, and an aluminum-boron alloy as a target. A boron-containing aluminum nitride thin film is formed by sputtering in an atmosphere, or a halide or hydride containing at least boron and aluminum, an organometallic compound, or a metal alkoxide is diluted with hydrogen or an inert gas and supplied as a raw material to form a plasma. It has been found that a method of forming a boron-containing aluminum nitride thin film by the CVD method is preferable. When the boron-containing aluminum nitride thin film is formed on the diamond single crystal by the above manufacturing method under appropriate conditions, a highly oriented or single crystal boron-containing aluminum nitride thin film can be obtained. The boron-containing aluminum nitride thus obtained can be used as deposited on the substrate, or if necessary after removing the substrate.
【０００８】[0008]
＜成膜方法（プロセス、原料、温度）＞ 窒化アルミニ
ウムや窒化ホウ素など合成中に窒素を結晶中に取り込む
ためには、窒素は分子状窒素（Ｎ2）の形態が非常に安
定であるために、窒素の活性度の高い雰囲気、つまり、
窒素の分圧が高いか窒素が原子やイオンなどの活性の高
い状態である必要がある。本発明の様に結晶性の高い薄
膜を合成する際には、総圧力が０．１気圧以下である減
圧下で行うことが好ましいので、窒素の活性度を高める
ために後者の方法を採用する事が必要である。本発明の
ホウ素含有窒化アルミニウムの合成に当たっては、原子
状窒素や窒素イオンの多量に存在する状態で行うのが好
ましい。つまり、スパッタ法やプラズマＣＶＤ法イオン
ビーム蒸着法、レーザアブレーション法などである。<Film Forming Method (Process, Raw Material, Temperature)> In order to incorporate nitrogen into the crystal during synthesis such as aluminum nitride and boron nitride, nitrogen has a very stable form of molecular nitrogen (N 2 ). , An atmosphere of highly active nitrogen, that is,
The partial pressure of nitrogen must be high or the nitrogen must be in a state of high activity such as atoms and ions. When synthesizing a thin film having high crystallinity as in the present invention, it is preferable to carry out under a reduced pressure with a total pressure of 0.1 atm or less. Therefore, the latter method is adopted to increase the activity of nitrogen. Things are needed. The synthesis of the boron-containing aluminum nitride of the present invention is preferably carried out in the presence of a large amount of atomic nitrogen or nitrogen ions. That is, a sputtering method, a plasma CVD method, an ion beam evaporation method, a laser ablation method, or the like is used.
【０００９】＜組成範囲＞ 膜中の各元素の組成はＢＡ
ｌＮ膜の有する機能性および結晶性で有用な範囲が決定
される。おおよその傾向としてＢxＡｌ1-xＮy であらわ
される組成のうちＢとＡｌの比率を決める値ｘが０．０
０１から０．２の範囲では、結晶性はＡｌＮ薄膜と同等
で非常に高品質のＢＡｌＮ膜が得られる。しかし、ｘが
０．００１未満のときはその機能的な物性もＡｌＮと変
わらないのでＢＡｌＮ膜としての有用性は無い。ｘが
０．２を越えると合成されたＢＡｌＮ膜の結晶性は低下
し、ｘが０．７を越えるとその結晶性は著しく失われＢ
ＡｌＮ膜としての機能を発揮することができなくなって
しまう。窒素の含有量を決める値ｙは１に等しいときが
もっともＢＡｌＮ膜の結晶性が良く欠陥が少ないと考え
られるが、発明者らの研究ではｙの値が０．８５から
１．０５の範囲ではＢＡｌＮ膜の機能を発現させること
ができる程度の結晶性を有していることがわかった。な
お、薄膜の厚さが１０ｎｍ未満であると、実用上の効果
に乏しくまた３０μｍを越えると薄膜の結晶性が低下す
るので、１０ｎｍ以上３０μｍ以下の範囲が好適であ
る。<Composition range> The composition of each element in the film is BA
The useful range of the functionality and crystallinity of the 1N film is determined. As a general tendency, the value x that determines the ratio of B and Al in the composition represented by B x Al 1-x N y is 0.0.
In the range of 01 to 0.2, the crystallinity is equivalent to that of the AlN thin film, and a very high quality BAlN film can be obtained. However, when x is less than 0.001, its functional physical properties are the same as those of AlN, so that it is not useful as a BAlN film. When x exceeds 0.2, the crystallinity of the synthesized BAlN film deteriorates, and when x exceeds 0.7, the crystallinity is significantly lost.
The function as the AlN film cannot be exerted. It is considered that the crystallinity of the BAlN film is the best and the number of defects is best when the value y that determines the nitrogen content is equal to 1, but in the study by the inventors, when the value of y is 0.85 to 1.05 It was found that the crystallinity was such that the function of the BAlN film could be exhibited. If the thickness of the thin film is less than 10 nm, the practical effect is poor, and if it exceeds 30 μm, the crystallinity of the thin film deteriorates. Therefore, the range of 10 nm or more and 30 μm or less is preferable.
【００１０】＜基材＞ ＢＡｌＮ膜を形成する際の基材
としては、成膜に必要な７００℃以上の温度に耐える材
料ならば何でも使用できるが、Ｂ、Ａｌ、Ｎとの反応性
に乏しい材料が好ましく、金属ではＭｏ、Ｗ、Ｎｉ、Ｔ
ａ、Ｎｂ、半導体ではダイヤモンド、Ｓｉ、Ｇｅ、Ａｌ
Ｎ、ＳｉＣ、ＧａＮ、ＢＰ、ＩｎＮ、その他の化合物で
はＡｌ2Ｏ3、ＳｉＯ2、ＭｇＯ、ＢｅＯなどが好まし
い。<Substrate> As the substrate for forming the BAlN film, any material can be used as long as it can withstand the temperature of 700 ° C. or higher required for film formation, but it has poor reactivity with B, Al and N. Preferred materials are Mo, W, Ni, T for metals
a, Nb, semiconductor: diamond, Si, Ge, Al
Among N, SiC, GaN, BP, InN and other compounds, Al 2 O 3 , SiO 2 , MgO, BeO and the like are preferable.
【００１１】配向性または単結晶ＢＡｌＮ薄膜を形成す
るためには、ＢＡｌＮ膜が基材の方位に従って成長する
ような材料を選択する必要があり、しかも基板材料が配
向性を有するか単結晶でなければならない。このような
基板材料としてはダイヤモンド、Ｓｉ、Ａｌ2Ｏ3、Ｓｉ
Ｃがある。単結晶を基板とする場合、薄膜を形成する基
板の結晶方位は３回または６回の対称性をもつ結晶面が
ホウ素含有窒化アルミニウム膜の結晶性がよくなりやす
いＣ面に配向するので好ましい。このような結晶面とは
ダイヤモンド、Ｓｉ、立方晶ＳｉＣの（１１１）面、α
ーＡｌ2Ｏ3、六方晶ＳｉＣのＣ面＜（０００１）面＞が
ある。上記の基板材料とＢＡｌＮ薄膜との間に中間層を
挿入することによって、ＢＡｌＮ膜の結晶性を高めるこ
とができる場合がある。In order to form an oriented or single crystal BAlN thin film, it is necessary to select a material in which the BAlN film grows according to the orientation of the substrate, and the substrate material must be oriented or single crystal. I have to. Such substrate materials include diamond, Si, Al 2 O 3 , Si
There is C. When a single crystal is used as the substrate, the crystal plane of the substrate on which the thin film is formed is preferably 3 or 6 times because the crystal planes having symmetry are oriented to the C plane, which tends to improve the crystallinity of the boron-containing aluminum nitride film. Such crystal planes are (111) planes of diamond, Si and cubic SiC, α
-Al 2 O 3 and C plane <(0001) plane> of hexagonal SiC. By inserting an intermediate layer between the above substrate material and the BAlN thin film, the crystallinity of the BAlN film may be improved in some cases.
【００１２】＜中間層＞ 中間層としてＡｌＮ、Ｓｉ
Ｃ、ＢＰ、ＧａＮなどのうち１種類以上を基材上に形成
してから、ＢＡｌＮを成膜すると、基材上に直接成膜す
るよりも結晶性が良いことがある。特にＳｉ単結晶上に
ＢＡｌＮを形成する場合には、これら４種類の材料はＳ
ｉとＢＡｌＮの中間の格子定数をもっているので、中間
層としてＳｉ上に形成することによってＢＡｌＮ薄膜中
の欠陥や歪みを低減しより高品質のＢＡｌＮ薄膜を得る
ことができる。Ｓｉ以外の基板でも効果があることが多
い。中間層としてはＡｌＮがもっとも好ましく、ＳｉＣ
がこれに次ぎ、ＢＰ、ＧａＮはこれらよりも効果が小さ
い。中間層の厚さは１ｎｍ以上１μｍ以下が適当な範囲
である。これ以上薄いと中間層が無い時と同等であり、
厚いと中間層自体に歪みや欠陥が発生するのでかえって
ＢＡｌＮ膜の結晶性を低下させる。<Intermediate layer> AlN, Si as an intermediate layer
When one or more kinds of C, BP, GaN, etc. are formed on a base material and then BAlN is deposited, the crystallinity may be better than when the film is directly formed on the base material. Especially when BAlN is formed on a Si single crystal, these four kinds of materials are S
Since it has a lattice constant intermediate between i and BAlN, by forming the intermediate layer on Si, defects and strain in the BAlN thin film can be reduced and a higher quality BAlN thin film can be obtained. Substrates other than Si are often effective. AlN is most preferable for the intermediate layer, and SiC
However, BP and GaN are less effective than these. The suitable thickness of the intermediate layer is 1 nm or more and 1 μm or less. If it is thinner than this, it is the same as when there is no intermediate layer,
If it is thick, distortion and defects occur in the intermediate layer itself, which rather reduces the crystallinity of the BAlN film.
【００１３】＜価電子制御＞ Ｓｉ、Ｃ、Ｓ、Ｓｅなど
の元素を成膜中にまたはイオン注入などの方法によって
ドーピングすることによってＮ型の導電性を有するＢＡ
ｌＮ膜を得ることができる。同様にＢｅ、Ｍｇ、Ｚｎ、
Ｃａなどの元素をドーピングすることによってＰ型のＢ
ＡｌＮ膜を得ることができる。これらの元素はＢＡｌＮ
膜の成膜中に各元素の単体、酸化物、ハロゲン化物、水
素化物、有機金属化合物を原料としてドーピングするこ
とができる。イオン注入法は注入後の結晶欠陥の回復が
困難なので好ましくない。<Valent Electron Control> BA having N-type conductivity by doping elements such as Si, C, S and Se during film formation or by a method such as ion implantation.
An IN film can be obtained. Similarly, Be, Mg, Zn,
P-type B by doping with elements such as Ca
An AlN film can be obtained. These elements are BAlN
During the formation of the film, simple substances of each element, oxides, halides, hydrides, and organometallic compounds can be used as raw materials for doping. The ion implantation method is not preferable because it is difficult to recover crystal defects after the implantation.
【００１４】[0014]
【実施例】単結晶Ｓｉ（１１１）を基板としてスパッタ
法によりホウ素含有窒化アルミニウム薄膜の合成を行っ
た。基板は１０ｍｍ角の単結晶Ｓｉ（１１１）を、純水
で５％に希釈した弗酸中に浸した後にアセトン洗浄して
用いた。スパッタ用のターゲットには金属アルミニウム
を減圧窒素中で溶融して窒化アルミニウム粉末１５重量
％、立方晶窒化ホウ素粉末１５重量％を分散した後に固
化したものを用いた。通常の高周波マグネトロンスパッ
タ装置に基板とターゲットを設置し、Ａｒ／Ｎ２を等量
に混合したガスを導入して総圧力が０．０５Ｔｏｒｒに
なるように調節した。基板を１１５０℃に加熱し、高周
波（１３．５６ＭＨｚ）出力３５０Ｗで１時間スパッタ
を行ったところ、厚さ０．４μｍの薄膜を得た。Example A boron-containing aluminum nitride thin film was synthesized by a sputtering method using single crystal Si (111) as a substrate. The substrate was used by immersing 10 mm square single crystal Si (111) in hydrofluoric acid diluted to 5% with pure water and then washing with acetone. As a target for sputtering, a target obtained by melting aluminum metal in vacuum nitrogen and dispersing 15% by weight of aluminum nitride powder and 15% by weight of cubic boron nitride powder and then solidifying was used. The substrate and the target were placed in a normal high frequency magnetron sputtering apparatus, and a gas in which Ar / N 2 was mixed in an equal amount was introduced to adjust the total pressure to 0.05 Torr. When the substrate was heated to 1150 ° C. and was sputtered at a high frequency (13.56 MHz) output of 350 W for 1 hour, a thin film having a thickness of 0.4 μm was obtained.
【００１５】この薄膜を２次イオン質量分析法で組成分
析を行うとＢ0.015Ａｌ0.985Ｎ0.97で表される組成であ
ることが判明した。Ｘ線回折法で観察したところではＣ
面からの回折線のみが観察されウルツ鉱型の高配向膜ま
たは単結晶膜であることが予想された。Ｘ線回折のロッ
キングカーブの半値幅は１．５度と高品質高配向性結晶
であった。更に高速反射電子線回折観察を実施すること
によりによりこの膜はウルツ鉱型の単結晶薄膜であるこ
とが明かになった。Composition analysis of this thin film by secondary ion mass spectrometry revealed that it had a composition represented by B0.015Al0.985N0.97. When observed by the X-ray diffraction method, C
Only the diffraction line from the plane was observed, and it was expected that the film was a wurtzite-type highly oriented film or a single crystal film. The full width at half maximum of the rocking curve of X-ray diffraction was 1.5 degrees, which was a high quality and highly oriented crystal. Further high-speed backscattering electron diffraction observation revealed that this film was a wurtzite type single crystal thin film.
【００１６】（比較例１） 実験例と同様に単結晶Ｓｉ
（１１１）を基板としてスパッタ法によりホウ素含有窒
化アルミニウム薄膜の合成を行った。基板は１０ｍｍ角
の単結晶Ｓｉ（１１１）を、純水で５％に希釈した弗酸
中に浸した後にアセトン洗浄して用いた。スパッタ用の
ターゲットには窒化アルミニウム粉末２０重量％、立方
晶窒化ホウ素粉末８０重量％を混合してプレスしたもの
を用いた。通常の高周波マグネトロンスパッタ装置に基
板とターゲットを設置し、Ａｒ／Ｎ２を等量に混合した
ガスを導入して総圧力が０．０５Ｔｏｒｒになるように
調節した。基板を１１５０℃に加熱し、高周波（１３．
５６ＭＨｚ）出力３５０Ｗで１時間スパッタを行ったと
ころ、厚さ０．３μｍの薄膜を得た。この薄膜を２次イ
オン質量分析法で組成分析を行うとＢ０．８３Ａｌ０．
１７Ｎ０．８０で表される組成であることが判明した。
Ｘ線回折法で観察したところ基板の回折線しか観察され
ず、結晶性を持たないアモルファス薄膜であると判断さ
れた。(Comparative Example 1) Single crystal Si as in the experimental example
A boron-containing aluminum nitride thin film was synthesized by a sputtering method using (111) as a substrate. The substrate was used by immersing 10 mm square single crystal Si (111) in hydrofluoric acid diluted to 5% with pure water and then washing with acetone. As a target for sputtering, an aluminum nitride powder 20% by weight and a cubic boron nitride powder 80% by weight were mixed and pressed. The substrate and the target were placed in a normal high frequency magnetron sputtering apparatus, and a gas in which Ar / N 2 was mixed in an equal amount was introduced to adjust the total pressure to 0.05 Torr. The substrate is heated to 1150 ° C., and a high frequency (13.
(56 MHz) Sputtering was performed for 1 hour at an output of 350 W, and a thin film having a thickness of 0.3 μm was obtained. When the composition analysis of this thin film was performed by secondary ion mass spectrometry, B0.83Al0.
It was found that the composition was 17N0.80.
When observed by an X-ray diffraction method, only the diffraction line of the substrate was observed, and it was judged that the film was an amorphous thin film having no crystallinity.
【００１７】[0017]
【実施例１】基板として３．５ｍｍ角の表面を平坦に研
摩した超高圧合成ダイヤモンド単結晶の（１１１）面を
用い、有機溶媒による洗浄とそれにつづく１０％塩化水
素水溶液による洗浄を行った後、表面水素終端処理を行
った。表面水素終端処理はマイクロ波プラズマＣＶＤ装
置を用い、水素ガスのみを装置内に供給し、圧力１００
Ｔｏｒｒ、マイクロ波電力４００Ｗにて１０分間行っ
た。ダイヤモンドの合成に用いられるマイクロ波プラズ
マＣＶＤ装置（特開昭５９−３０９８）に基板を設置
し、ジボラン（Ｂ２Ｈ６）１％、塩化アルミニウム（Ａ
ｌＣｌ３）４％、水素４５％、残りアルゴンを混合した
ガスを導入して総圧力が５Ｔｏｒｒになるように調節し
た。マイクロ波（２．４５ＧＨｚ）出力８００Ｗでプラ
ズマを発生させながら基板を１１５０℃に加熱し、１時
間成長を行ったところ、厚さ１．２μｍの硼素含有窒化
アルミニウム薄膜を得た。Example 1 (111) plane of ultra-high pressure synthetic diamond single crystal whose surface was 3.5 mm square was polished as a substrate, and after cleaning with an organic solvent and subsequent cleaning with 10% hydrogen chloride aqueous solution , Surface hydrogen termination treatment was performed. For the surface hydrogen termination treatment, a microwave plasma CVD apparatus is used and only hydrogen gas is supplied into the apparatus at a pressure of 100.
Torr was performed at a microwave power of 400 W for 10 minutes. The substrate was placed in a microwave plasma CVD apparatus (Japanese Patent Laid-Open No. 59-3098) used for synthesizing diamond, and 1% diborane (B 2 H 6 ) and aluminum chloride (A
lCl 3) 4%, 45% hydrogen, the total pressure by introducing a mixture of the remainder argon gas was adjusted to 5 Torr. The substrate was heated to 1150 ° C. while generating plasma with a microwave (2.45 GHz) output of 800 W and was grown for 1 hour to obtain a boron-containing aluminum nitride thin film having a thickness of 1.2 μm.
【００１８】この薄膜を２次イオン質量分析法で組成分
析を行うとＢ0.08Ａｌ0.92Ｎ1.00で表される組成である
ことが判明した。Ｘ線回折法で観察したところではＣ面
からの回折線のみが観察されウルツ鉱型の高配向膜また
は単結晶膜であることが予想された。Ｘ線回折のロッキ
ングカーブの半値幅は３．２度と高配向性結晶であっ
た。更に高速反射電子線回折観察を実施することにより
によりこの膜はウルツ鉱型の配向性薄膜であることが明
かになった。Composition analysis of this thin film by secondary ion mass spectrometry revealed that it had a composition represented by B0.08Al0.92N1.00. When observed by the X-ray diffraction method, only the diffraction line from the C plane was observed, and it was expected that the film was a wurtzite highly oriented film or a single crystal film. The full width at half maximum of the rocking curve of X-ray diffraction was 3.2 degrees, which was a highly oriented crystal. Further high-speed reflection electron beam diffraction observation revealed that this film was a wurtzite type oriented thin film.
【００１９】[0019]
【発明の効果】本発明によれば窒化アルミニウムよりも
高い硬度、広いバンドギャップ、大きな音速、を有し価
電子制御が容易で、結晶性のよいホウ素含有窒化アルミ
ニウム薄膜を容易に得ることができる。According to the present invention, a boron-containing aluminum nitride thin film having higher hardness than aluminum nitride, a wide band gap, a large sound velocity, easy valence electron control, and good crystallinity can be easily obtained. .
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭47−1370（ＪＰ，Ａ) 特開 昭59−217700（ＪＰ，Ａ) 特開 平３−10074（ＪＰ，Ａ) 特開 平５−255848（ＪＰ，Ａ) 特開 平７−267787（ＪＰ，Ａ) 特開 昭59−3098（ＪＰ，Ａ) 特開 平１−232695（ＪＰ，Ａ) 特開 平６−316402（ＪＰ，Ａ) 特開 平７−232998（ＪＰ，Ａ) 特開 平８−239752（ＪＰ，Ａ) 特開 平９−125229（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C30B 1/00 - 35/00 C01B 21/064 C01B 21/072 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ) ＥＵＲＯＰＡＴ（ＱＵＥＳＴＥＬ)─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-47-1370 (JP, A) JP-A-59-217700 (JP, A) JP-A-3-10074 (JP, A) JP-A-5- 255848 (JP, A) JP 7-267787 (JP, A) JP 59-3098 (JP, A) JP 1-232695 (JP, A) JP 6-316402 (JP, A) JP-A-7-232998 (JP, A) JP-A-8-239752 (JP, A) JP-A-9-125229 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C30B 1/00-35/00 C01B 21/064 C01B 21/072 CA (STN) REGISTRY (STN) EUROPAT (QUESTEL)
Claims (4)
０．７、０．８５≦ｙ≦１．０５）なる組成と、ウルツ
鉱型結晶構造を有し、厚さ１０ｎｍ以上３０μｍ以下で
あり、ダイヤモンド単結晶基板上に形成されてなること
を特徴とする硼素含有窒化アルミニウム薄膜。1. B x Al 1-x N y (0.001 ≦ x ≦
0.7, 0.85 ≦ y ≦ 1.05), a wurtzite type crystal structure, a thickness of 10 nm or more and 30 μm or less, and being formed on a diamond single crystal substrate. Boron-containing aluminum nitride thin film.
性であるかまたは単結晶であることを特徴とする請求項
１記載の硼素含有窒化アルミニウム薄膜。2. The boron-containing aluminum nitride thin film according to claim 1, wherein the boron-containing aluminum nitride is highly oriented or is a single crystal.
ム、窒化ホウ素、アルミニウム−ホウ素合金の中から選
ばれた材料をターゲットとして、窒素またはアンモニア
を含むガス雰囲気で、スパッタ法によってＢｘＡｌ
１−ｘＮｙ（０．００１≦ｘ≦０．７、０．８５≦ｙ≦
１．０５）の硼素含有窒化アルミニウム薄膜を、ダイヤ
モンド単結晶基板上に形成することを特徴とする硼素含
有窒化アルミニウム薄膜の製造方法。3. A target material selected from aluminum, boron, aluminum nitride, boron nitride, and an aluminum-boron alloy is used as a target in a gas atmosphere containing nitrogen or ammonia to sputter B x Al.
1-x N y (0.001 ≦ x ≦ 0.7, 0.85 ≦ y ≦
The boron-containing aluminum nitride thin film of 1.05), diamond
A method for producing a boron-containing aluminum nitride thin film, which comprises forming on a Mondo single crystal substrate.
ロゲン化物または水素化物または有機金属化合物、金属
アルコキシドを水素または不活性ガスで希釈して原料と
して供給し、プラズマＣＶＤ法によってＢｘＡｌ１−ｘ
Ｎｙ（０．００１≦ｘ≦０．７、０．８５≦ｙ≦１．０
５）の硼素含有窒化アルミニウム薄膜を、ダイヤモンド
単結晶基板上に形成することを特徴とする硼素含有窒化
アルミニウム薄膜の製造方法。4. A halide or hydride containing boron and aluminum, an organometallic compound, or a metal alkoxide is diluted with hydrogen or an inert gas and supplied as a raw material, and B x Al 1-x is formed by a plasma CVD method.
N y (0.001 ≦ x ≦ 0.7, 0.85 ≦ y ≦ 1.0
The boron-containing aluminum nitride thin film of 5) is replaced with diamond.
A method for producing a boron-containing aluminum nitride thin film, which comprises forming on a single crystal substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11652494A JP3465345B2 (en) | 1994-05-30 | 1994-05-30 | Boron-containing aluminum nitride thin film and manufacturing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11652494A JP3465345B2 (en) | 1994-05-30 | 1994-05-30 | Boron-containing aluminum nitride thin film and manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07315998A JPH07315998A (en) | 1995-12-05 |
| JP3465345B2 true JP3465345B2 (en) | 2003-11-10 |
Family
ID=14689268
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|---|---|---|---|
| JP11652494A Expired - Fee Related JP3465345B2 (en) | 1994-05-30 | 1994-05-30 | Boron-containing aluminum nitride thin film and manufacturing method |
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| Country | Link |
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|---|---|---|---|---|
| EP0730044B1 (en) * | 1995-03-01 | 2001-06-20 | Sumitomo Electric Industries, Limited | Boron-aluminum nitride coating and method of producing same |
| WO2014087799A1 (en) * | 2012-12-05 | 2014-06-12 | 株式会社村田製作所 | Piezoelectric member, elastic wave apparatus, and piezoelectric member manufacturing method |
| JP6932995B2 (en) * | 2017-05-23 | 2021-09-08 | Tdk株式会社 | Nitride single crystal |
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| JPH07315998A (en) | 1995-12-05 |
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