JPH09320964A - Manufacture of compound semiconductor - Google Patents
Manufacture of compound semiconductorInfo
- Publication number
- JPH09320964A JPH09320964A JP13176796A JP13176796A JPH09320964A JP H09320964 A JPH09320964 A JP H09320964A JP 13176796 A JP13176796 A JP 13176796A JP 13176796 A JP13176796 A JP 13176796A JP H09320964 A JPH09320964 A JP H09320964A
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- JP
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- Prior art keywords
- protective film
- growth
- compound semiconductor
- stripe
- gas
- Prior art date
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- Recrystallisation Techniques (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水素化物および有
機金属を原料とする化合物半導体薄膜の気相成長におい
て、化合物半導体層を形成する方法に係わり、特に選択
成長用保護膜への堆積を抑制するのに適した化合物半導
体の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming a compound semiconductor layer in vapor phase growth of a compound semiconductor thin film made of a hydride and an organic metal as a raw material, and particularly to suppressing deposition on a protective film for selective growth. The present invention relates to a method for producing a compound semiconductor suitable for
【０００２】[0002]
【従来の技術】最近の化合物半導体の素子構造を最適化
させる技術のひとつとして選択成長が用いられている
が、ＭＢＥ法では選択成長は困難であるため、通常ＭＯ
ＣＶＤ法が用いられている。ＭＯＣＶＤ法の選択成長に
おける利点としては、基板またはエピタキシャル成長層
へのダメージが殆どないことおよび比較的低温でプロセ
スが行えるため、品質の高い選択成長領域が得られるこ
とにある。2. Description of the Related Art Recently, selective growth has been used as one of the techniques for optimizing the device structure of compound semiconductors. However, since selective growth is difficult with the MBE method, it is usually MO.
The CVD method is used. The advantages of the MOCVD method in selective growth are that there is almost no damage to the substrate or the epitaxial growth layer and that the process can be performed at a relatively low temperature, so that a high-quality selective growth region can be obtained.
【０００３】しかしながら、選択成長を行う際には、保
護膜上に多結晶の堆積が起こらないようにするため、成
長条件、混晶比、およびマスク幅等に大きな制約を受け
ていた。特に、Ａｌを含んだ化合物の場合には、Ａｌの
混晶比を上げるほど、そしてマスク幅を大きくするほ
ど、保護膜上に多結晶が堆積しやすくなるという問題が
あった。この解決方法としては、選択成長を行う際に成
長させる化合物の母体元素を含まないハライド法および
／またはハロゲンガスを加えることにより広い範囲にわ
たり保護膜上への多結晶の堆積が回避できることが報告
されている（ＷＯ９３／０１６１４）。However, when selective growth is performed, growth conditions, mixed crystal ratios, mask widths, etc. are greatly restricted in order to prevent polycrystal deposition on the protective film. In particular, in the case of a compound containing Al, there is a problem that the higher the mixed crystal ratio of Al and the larger the mask width, the easier the polycrystal is deposited on the protective film. As a solution to this problem, it has been reported that the deposition of polycrystals on the protective film can be avoided over a wide range by adding a halide method and / or a halogen gas which does not include the host element of the compound to be grown during the selective growth. (WO93 / 01614).
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、この上
記の手法を用いてもまだ選択性が十分でない場合があっ
た。特に、保護膜で保護される領域が広い場合や、保護
膜に対して選択成長を行いたい領域が極端に狭い場合に
選択性が十分でない場合がある。However, there are cases where the selectivity is not sufficient even when the above method is used. In particular, the selectivity may not be sufficient when the area protected by the protective film is large or when the area where selective growth is desired to be performed on the protective film is extremely narrow.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、上記の課
題を解決すべく鋭意検討した結果、ハライドガスおよび
／またはハロゲンガスを加えて選択成長を行う際に、特
定の結晶成長面と保護膜の方向を選択することにより、
選択性を向上し得ることを見出し、本発明に到達した。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that when a selective growth is performed by adding a halide gas and / or a halogen gas, By selecting the direction of the protective film,
The inventors have found that selectivity can be improved and have reached the present invention.
【０００６】即ち、本発明の要旨は、III-Ｖ族化合物半
導体単結晶の｛１００｝面に、ストライプ状の保護膜を
＜０１１＞Ｂ方向を中心として±４５°以内の方向に形
成した後、III-Ｖ族化合物半導体の原料ガスとともにハ
ライドガスおよび／またはハロゲンガスを添加して、保
護膜が形成されていない部分にIII-Ｖ族化合物半導体単
結晶薄膜を選択成長させる工程を含むことを特徴とする
化合物半導体の製造方法に存する。That is, the gist of the present invention is that after forming a stripe-shaped protective film on the {100} plane of a III-V group compound semiconductor single crystal in a direction within ± 45 ° centering on the <011> B direction. , A step of adding a halide gas and / or a halogen gas together with a source gas of a III-V group compound semiconductor to selectively grow a III-V group compound semiconductor single crystal thin film in a portion where a protective film is not formed. The present invention resides in a method for producing a characteristic compound semiconductor.
【０００７】[0007]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明においては、III-Ｖ族化合物半導体単結晶の｛１
００｝ジャストの面上に選択成長を行うこととし、オフ
アングルはあっても０．５°以下とする。これにより、
リッジやグルーブ等の構造を高精度に作り込むことが可
能である。即ち、レーザの様に光を閉じ込める装置の場
合で、特に高出力が求められる場合等には、非常に対称
性の高いリッジやグルーブ等の構造を作り込むことが必
要となり、オフアングルに垂直な方向にリッジやグルー
ブ等の構造を作成する場合には対称性に狂いが生じてし
まうが、ジャストの面を成長面として用いることによ
り、どの様な方向に構造を作成してもその様な問題を回
避できる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the present invention, the group III-V compound semiconductor single crystal {1
00} Just growth is performed on the surface, and the off angle is 0.5 ° or less. This allows
Structures such as ridges and grooves can be built in with high precision. That is, in the case of a device for confining light such as a laser, particularly when a high output is required, it is necessary to form a structure such as a ridge or a groove having a very high symmetry, which is perpendicular to the off angle. When a structure such as a ridge or groove is created in a certain direction, the symmetry will be out of order, but using the just surface as a growth surface will cause such a problem even if the structure is created in any direction. Can be avoided.
【０００８】この｛１００｝面上で選択成長を行うた
め、窒化珪素、酸化珪素等公知の材料および方法を用い
て保護膜を設けるが、選択性よく成長を行うには、｛１
００｝面上でストライプ状の保護膜を＜０１１＞Ｂ方向
を中心として±４５°以内、好ましくは±３０°以内の
方向に配置する。ここで＜０１１＞Ｂ方向とは、Ｖ族元
素が表面に出ている｛１１１｝Ｂ面の法線の｛１００｝
面上への正射影の方向のことである。即ち、図１ａに示
す（１００）面に対しては[０−１１]および[０１−１]
で表される方向であって、この方向に形成したストライ
プ状保護膜を図１ｂに示した。他の｛１００｝面につい
ても、それぞれについてこれと結晶学的に等価な方向を
選べばよい。なお、これに対して、III族元素が表面に
出ている｛１１１｝Ａ面の法線の｛１００｝面上への正
射影の方向のことを＜０１１＞Ａ方向という。In order to carry out selective growth on this {100} plane, a protective film is provided using a known material and method such as silicon nitride and silicon oxide. In order to carry out selective growth, {1
The stripe-shaped protective film on the {00} plane is arranged within ± 45 °, preferably ± 30 °, with the <011> B direction as the center. Here, the <011> B direction means {100} of the normal line of the {111} B plane on which the group V element is exposed.
It is the direction of orthographic projection onto a surface. That is, for the (100) plane shown in FIG. 1a, [0-11] and [01-1]
The stripe-shaped protective film formed in this direction is shown in FIG. 1b. For the other {100} planes as well, a direction crystallographically equivalent to this may be selected. On the other hand, the direction of the orthogonal projection of the normal line of the {111} A plane onto the {100} plane where the group III element appears on the surface is referred to as the <011> A direction.
【０００９】また、かかるストライプ状の保護膜は、短
辺の幅が５０μｍ以上で、かつ｛１００｝面上で薄膜形
成領域に対する保護膜形成領域の割合が１以上、好まし
くは２以上、最も好ましくは２．５以上となる様に形成
するのが好ましいことがある。即ち、ブロードエリアの
レーザ等を製造する場合や、局所的に成長速度を上げる
必要がある場合等にその様な保護膜形成領域が大きく、
成長領域を狭くすることが要求され、その場合、一般に
選択性は著しく低下するが、本発明によれば、保護膜の
方位を選ぶことにより、選択性よく成長を行うことがで
きる。In this stripe-shaped protective film, the width of the short side is 50 μm or more, and the ratio of the protective film forming region to the thin film forming region on the {100} plane is 1 or more, preferably 2 or more, and most preferably. In some cases, it is preferable to form it so that it is 2.5 or more. That is, when manufacturing a broad area laser or the like, or when it is necessary to locally increase the growth rate, such a protective film formation region is large,
It is required to narrow the growth region, and in that case, the selectivity is generally significantly lowered. However, according to the present invention, the growth can be performed with high selectivity by selecting the orientation of the protective film.
【００１０】本発明で用いる化合物半導体の原料ガスと
しては、有機金属、水素化物、塩化物等公知のいずれの
ものも使用可能であり、有機金属としてはトリメチルガ
リスム（ＴＭＧ）、トリエチルガリウム（ＴＥＧ）、ト
リメチルアルミニウム（ＴＭＡ）およびトリエチルイン
ジウム（ＴＭＩ）等が、水素化物としてはアルシン（Ａ
ｓＨ3）およびホスフィン（ＰＨ３）等が、塩化物とし
ては塩化ガリウム（ＧａＣｌ）、ジエチルガリウムクロ
ライド（ＤＥＧａＣｌ）および三塩化砒素（ＡｓＣ
ｌ3）等が用いられるが、これらの中でも成長機構が比
較的簡単で、精密な成長速度の制御が比較的容易に行え
る等の点で、塩素を含まない有機金属および塩素を含ま
ない水素化物が好ましい。また、特に有機金属を用いる
場合に、本発明の選択性向上の効果は大きい。As the raw material gas for the compound semiconductor used in the present invention, any known gas such as organic metal, hydride and chloride can be used, and as the organic metal, trimethyl galism (TMG) and triethyl gallium (TEG) are used. ), Trimethylaluminum (TMA), triethylindium (TMI) and the like are arsine (A
sH 3 ) and phosphine (PH 3) are chlorides such as gallium chloride (GaCl), diethyl gallium chloride (DEGaCl) and arsenic trichloride (AsC).
l 3 ), etc. are used. Among them, chlorine-free organometals and chlorine-free hydrides are preferred because of their relatively simple growth mechanism and relatively easy precise control of growth rate. Is preferred. Further, the effect of improving the selectivity of the present invention is great especially when an organic metal is used.
【００１１】ハライドガスとしてはＨＢｒ、ＨＩ、Ｈ
Ｆ、ＨＣｌ等のハロゲン化水素やＣＣｌ2Ｆ2等のハロゲ
ン化炭素が、ハロゲンガスとしてはＣｌ2、Ｉ2、Ｆ2、
Ｂｒ2など、およびこれらの混合物が挙げられ、望まし
くはＨＣｌがよい。なお、原料ガスとして上記の塩化物
を用いた場合であって、Ａｌ混晶比が０．３〜０．４以
下の化合物半導体単結晶薄膜を成長させる場合には、別
途ハライドガスまたはハロゲンガスを導入しなくても、
ある程度選択性よく成長を行うことができる。As the halide gas, HBr, HI, H
Hydrogen halides such as F and HCl, and carbon halides such as CCl 2 F 2 can be used as halogen gas such as Cl 2 , I 2 , F 2 ,
Br 2 and the like, and mixtures thereof, and preferably HCl. In addition, when the above-mentioned chloride is used as the source gas and a compound semiconductor single crystal thin film having an Al mixed crystal ratio of 0.3 to 0.4 is grown, a halide gas or a halogen gas is separately added. Without introducing
Growth can be performed with some selectivity.
【００１２】これらのハライドガスおよび／またはハロ
ゲンガスの使用量は成長室の大きさ、成長温度、成長圧
力、使用する原料の種類等に依存するが、量が多すぎる
と薄膜成長が止まり、エッチングになってしまうエッチ
ングモード域となり、量が少なすぎると保護膜上に多結
晶が成長するデポジションモード域となるので、ハライ
ドガスおよび／またはハロゲンガスの流量を適宜調節し
てこれらの領域を避け、選択成長を行いたい領域には結
晶が成長するが、保護膜上には多結晶が成長しないセレ
クティブモードで成長を行うこととする。The amount of these halide gas and / or halogen gas used depends on the size of the growth chamber, the growth temperature, the growth pressure, the type of raw material used, etc., but if the amount is too large, the thin film growth stops and etching occurs. It becomes the etching mode area which becomes, and when it is too small, it becomes the deposition mode area where the polycrystal grows on the protective film. Therefore, adjust the flow rate of halide gas and / or halogen gas appropriately to avoid these areas. It is assumed that crystals grow in a region where selective growth is desired, but growth is performed in a selective mode in which polycrystal does not grow on the protective film.
【００１３】成長を行う際のガスの全圧は常圧以下が望
ましく、成長温度については一般に気相成長で用いられ
る条件でよく、一般的には５００〜９００℃程度だが、
低温側では選択性が低下する傾向にあり、一方あまりに
高温だとIII-Ｖ族元素の再蒸発や不純物の取り込みが問
題となる場合があるので、６００〜８５０℃、より好ま
しくは６５０〜８００℃程度がよい。ただし、本発明の
効果、即ち面方位や保護膜形成の方向による選択性の向
上効果はより低温側、即ち５００〜７００℃程度で顕著
であって、本発明は比較的穏やかな条件で効果的に選択
成長を行える点でも有用である。The total pressure of the gas during the growth is preferably atmospheric pressure or less, and the growth temperature may be the conditions generally used in the vapor phase growth, generally about 500 to 900 ° C.
On the low temperature side, the selectivity tends to decrease, and on the other hand, if it is too high, re-evaporation of III-V group elements and incorporation of impurities may become a problem, so 600 to 850 ° C., more preferably 650 to 800 ° C. The degree is good. However, the effect of the present invention, that is, the effect of improving the selectivity depending on the plane orientation and the direction of forming the protective film is remarkable on the lower temperature side, that is, about 500 to 700 ° C., and the present invention is effective under relatively mild conditions. It is also useful in that selective growth can be performed.
【００１４】本発明の製造方法は通常のIII-Ｖ族化合物
半導体薄膜の成長に有効であるが、特にアルミニウムを
含むIII-Ｖ族化合物半導体の成長に適している。具体的
には、ＡｌＩｎＧａＰ、ＩｎＡｌＡｓ、ＡｌＩｎＰ、Ａ
ｌＧａＡｓなどであり、特にＡｌＧａＡｓへは好適であ
る。The manufacturing method of the present invention is effective for the growth of ordinary III-V compound semiconductor thin films, but is particularly suitable for the growth of III-V compound semiconductors containing aluminum. Specifically, AlInGaP, InAlAs, AlInP, A
lGaAs and the like, and particularly suitable for AlGaAs.
【００１５】[0015]
【実施例】以下、本発明を実施例により更に詳細に説明
するが、本発明は、その要旨を越えない限り、下記実施
例により限定されるものではない。 （実施例）表面が（１００）面であるＧａＡｓ基板上
に、窒化珪素からなる幅３００μｍのストライプ状の保
護膜を、長辺の方向が[０−１１]方向（図１ｂ）となる
様に１００μｍ間隔で多数形成した後、ＭＯＶＰＥ法に
より膜厚約０．５μｍのＡｌ 0.3Ｇａ0.7Ａｓ層を選択成
長させて化合物半導体を製造した。原料ガスとしては、
トリメチルガリウム（ＴＭＧ）２．７×１０-4mol/mi
n、トリメチルアルミニウム（ＴＭＡ）１．０×１０-4m
ol/minおよびアルシン（ＡｓＨ3）２５０sccm(standard
cubic cm per minute)を、キャリアガスとしての水素
とともにガスの総流量が２２slm(standard cubic liter
per minute)となるように供給し、成長温度は６６０
℃、成長圧力は１３３ｈＰａとし、成長中に塩化水素を
４ｃｃ添加した。成長終了後、微分干渉光学顕微鏡で観
察したところ、保護膜中央部に多結晶の堆積が多少観察
されただけであった。 （比較例）長辺の方向が[０１１]方向（図１ｃ）となる
様に保護膜を形成した以外は実施例と全く同様にしたと
ころ、保護膜の端部を除く大部分に多結晶の堆積が観察
された。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
However, the present invention is not limited to the following
It is not limited by example. (Example) On a GaAs substrate having a (100) surface
A stripe-shaped protective layer made of silicon nitride with a width of 300 μm.
The direction of the long side of the protective film is the [0-11] direction (Fig. 1b).
After forming a large number at 100 μm intervals, MOVPE method
Al with a film thickness of about 0.5 μm 0.3Ga0.7Select As layer
Then, a compound semiconductor was manufactured. As the source gas,
Trimethylgallium (TMG) 2.7 × 10-Fourmol / mi
n, trimethyl aluminum (TMA) 1.0 x 10-Fourm
ol / min and arsine (AsHThree) 250sccm (standard
cubic cm per minute) as hydrogen as carrier gas
And the total gas flow rate is 22 slm (standard cubic liter)
per minute) and the growth temperature is 660
℃, growth pressure 133hPa, during the growth of hydrogen chloride
4 cc was added. After growth, view with a differential interference microscope.
As a result of observation, some polycrystal deposition was observed in the central part of the protective film.
It was only done. (Comparative example) The direction of the long side is the [011] direction (Fig. 1c).
Except that a protective film was formed in the same manner as in Example
Approximately, the deposition of polycrystals is observed on most of the protective film except the edges.
Was done.
【００１６】[0016]
【発明の効果】本発明によれば、保護膜上への多結晶の
堆積がなく、成長領域にのみ選択性よくIII-Ｖ族化合物
半導体薄膜の成長を行うことができる。According to the present invention, it is possible to grow a group III-V compound semiconductor thin film only in the growth region with good selectivity without depositing a polycrystal on the protective film.
【図１】ａはIII-Ｖ族化合物半導体単結晶の面方位を示
す模型の（１００）面側から見た上面図。ｂは実施例に
おいて＜０１１＞Ｂ方向に形成されたストライプ状保護
膜の方向の説明図。ｃは比較例において＜０１１＞Ａ方
向に形成されたストライプ状保護膜の方向の説明図。FIG. 1A is a top view of a model showing the plane orientation of a III-V compound semiconductor single crystal as seen from the (100) plane side. b is an explanatory view of the direction of the stripe-shaped protective film formed in the <011> B direction in the example. c is an explanatory view of the direction of the stripe-shaped protective film formed in the <011> A direction in the comparative example.
Ａ．III族元素が表面となる面 Ｂ．Ｖ族元素が表面となる面 １．ストライプ状保護膜 A. Surface where Group III element is the surface B. A surface on which the group V element is the surface 1. Striped protective film
───────────────────────────────────────────────────── フロントページの続き (72)発明者 後藤 秀樹 茨城県牛久市東猯穴町1000番地 三菱化学 株式会社筑波事業所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideki Goto 1000, Higashihuinana-cho, Ushiku-shi, Ibaraki Mitsubishi Chemical Corporation Tsukuba Plant
Claims (4)
０｝面に、ストライプ状の保護膜を＜０１１＞Ｂ方向を
中心として±４５°以内の方向に形成した後、III-Ｖ族
化合物半導体の原料ガスとともにハライドガスおよび／
またはハロゲンガスを添加して、保護膜が形成されてい
ない部分にIII-Ｖ族化合物半導体単結晶薄膜を選択成長
させる工程を含むことを特徴とする化合物半導体の製造
方法。1. A III-V compound semiconductor single crystal {10
0} plane, a stripe-shaped protective film is formed within ± 45 ° with the <011> B direction as the center, and then a halide gas and //
Alternatively, a method for producing a compound semiconductor, including a step of adding a halogen gas to selectively grow a III-V group compound semiconductor single crystal thin film in a portion where a protective film is not formed.
はハロゲン化炭素である請求項１の方法。2. The method according to claim 1, wherein the halide gas is hydrogen halide or carbon halide.
が５０μｍ以上でかつ｛１００｝面の薄膜形成領域に対
する保護膜形成領域の割合が１以上となる様に形成する
請求項１乃至２の方法。3. The striped protective film is formed so that the width of the short side is 50 μm or more and the ratio of the protective film forming region to the thin film forming region of the {100} plane is 1 or more. Method 2.
である請求項１乃至３の方法。4. The selective growth temperature is 500 to 900 ° C.
The method of claims 1 to 3, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13176796A JPH09320964A (en) | 1996-05-27 | 1996-05-27 | Manufacture of compound semiconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13176796A JPH09320964A (en) | 1996-05-27 | 1996-05-27 | Manufacture of compound semiconductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09320964A true JPH09320964A (en) | 1997-12-12 |
Family
ID=15065696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13176796A Pending JPH09320964A (en) | 1996-05-27 | 1996-05-27 | Manufacture of compound semiconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09320964A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7855096B2 (en) | 2007-09-28 | 2010-12-21 | Mitsubishi Electric Corporation | Method for manufacturing semiconductor device |
-
1996
- 1996-05-27 JP JP13176796A patent/JPH09320964A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7855096B2 (en) | 2007-09-28 | 2010-12-21 | Mitsubishi Electric Corporation | Method for manufacturing semiconductor device |
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