JPH02230722A - Vapor growth method of compound semiconductor - Google Patents
Vapor growth method of compound semiconductorInfo
- Publication number
- JPH02230722A JPH02230722A JP4991189A JP4991189A JPH02230722A JP H02230722 A JPH02230722 A JP H02230722A JP 4991189 A JP4991189 A JP 4991189A JP 4991189 A JP4991189 A JP 4991189A JP H02230722 A JPH02230722 A JP H02230722A
- Authority
- JP
- Japan
- Prior art keywords
- group
- raw material
- region
- substrate
- chloride
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000004065 semiconductor Substances 0.000 title claims description 15
- 150000001875 compounds Chemical class 0.000 title claims description 14
- 239000000758 substrate Substances 0.000 claims abstract description 49
- 239000013078 crystal Substances 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 20
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000012159 carrier gas Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 238000001947 vapour-phase growth Methods 0.000 claims description 7
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- 229910021478 group 5 element Inorganic materials 0.000 claims 2
- 238000003877 atomic layer epitaxy Methods 0.000 abstract description 34
- 239000007789 gas Substances 0.000 abstract description 16
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 abstract description 9
- 229910000070 arsenic hydride Inorganic materials 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 229910001218 Gallium arsenide Inorganic materials 0.000 abstract description 8
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 abstract 4
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- 238000010926 purge Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002052 molecular layer Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 101100215641 Aeromonas salmonicida ash3 gene Proteins 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910005260 GaCl2 Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- OTRPZROOJRIMKW-UHFFFAOYSA-N triethylindigane Chemical compound CC[In](CC)CC OTRPZROOJRIMKW-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は化合物半導体の気相成長方法に関し、さらに詳
しくは原子層エピタキシ（ ＡＬＥ ： ａｔｏｍｉｃ
ａｙｅｒ ｅｐｌｔａＸＶ）に関するもので、特に従来
の■族元素の塩化物を用いた高純度結晶成長が可能な塩
化物ＡＬＥと、簡便な原料輸送ができる有機金属を原料
とする８０ （ｍｅｔａｌ ｏｒｇａｎｉｃ ） −Ａ
ＬＥの特徴を両方備え持った新しいＡＬＥ成長方法に関
するもので必る。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for vapor phase growth of compound semiconductors, and more specifically to atomic layer epitaxy (ALE).
ayer eplta
It must be related to a new ALE growth method that has both the characteristics of LE.
［従来の技術およびその課題］
■−ｖ族化合物半導体のＡＬＥ成長方法としては、Ｇａ
（，ｐのような■族元素の塩化物を用いる方法（クロラ
イドＡＬＥ法）と、Ｇａ （ＣＨ３ ） ３ （ｔｒｉ
−ｍｅｔｈｙｌｇａｌ Ｉ ｉｕｍ：ＴＨＧ）のような
■族元素有機金属を用いる方法（ ８０−ＡＬＥ法）が
試みられてきた。[Prior art and its problems] As an ALE growth method for -v group compound semiconductors, Ga
(, p) (chloride ALE method) and Ga (CH3) 3 (tri
A method (80-ALE method) using a group Ⅰ element organic metal such as -methylgal Iium (THG) has been attempted.
これらの方法について図面を用いて簡単に説明する。These methods will be briefly explained using drawings.
第２図はＧａＣＩｌ−＾ｓＨ３ − Ｈ２系による２室
反応管を用いたＧａＡＳの塩化物ＡＬＥ成長装置の概略
構成図である。この方法では、上部反応管２１上流部に
Ｇａ金属用のソースポート２２を設置し、塩化水素との
反応によってＧａＣｆ！を生じせしめ、水素キャリアガ
スによって基板領域に輸送する。一方、ＡｓＨ３を下部
反応管２３に導入する。このガスは基板領域に達するま
でに反応管の熱によってほぼＡｓ４に分解する。基板結
晶２４はこの２つの反応管の間を移動する。図中、２６
に基板ホルダ２７の軌跡を示した。FIG. 2 is a schematic diagram of a GaAS chloride ALE growth apparatus using a two-chamber reaction tube based on the GaCl-^sH3-H2 system. In this method, a source port 22 for Ga metal is installed upstream of the upper reaction tube 21, and GaCf! is generated and transported to the substrate region by a hydrogen carrier gas. Meanwhile, AsH3 is introduced into the lower reaction tube 23. This gas is almost decomposed into As4 by the heat of the reaction tube before reaching the substrate region. The substrate crystal 24 moves between the two reaction tubes. In the figure, 26
2 shows the trajectory of the substrate holder 27.
このプロセスに従って基板結晶表面がＧａＣＪ２、Ａｓ
４雰囲気に交互に晒され、１サイクルでＧａＡｓの１分
子層単位の成長が生ずる。According to this process, the substrate crystal surface becomes GaCJ2, As
The substrate is exposed alternately to four atmospheres, and one cycle of growth causes growth of one molecular layer of GaAs.
この塩化物ＡＬＥ法の特徴として、次のような点が挙げ
られる。まず、ＧａＣｉＪが広い基板温度、ＧａＣＪｌ
流量範囲で極めて安定な単層吸着層を形成するために、
１分子層単位の成長が後で述べる有機金属を用いるＡＬ
Ｅ法に比較して実坦しやすい。ざらに、この塩化物ＡＬ
Ｅ法では重金属を含む不純物が原料に用いる塩化水素に
より、蒸発可能な塩化物に変換されるために結晶中に取
り込まれにくくなり、その結果、高純度の結晶が得られ
る、などである。Characteristics of this chloride ALE method include the following points. First, GaCiJ has a wide substrate temperature, GaCJl
To form an extremely stable monolayer adsorption layer over a range of flow rates,
AL using organic metals, which will be described later in terms of single-molecular-layer growth
Easier to achieve results than E method. In general, this chloride AL
In Method E, impurities containing heavy metals are converted into evaporable chloride by the hydrogen chloride used as a raw material, making them difficult to incorporate into the crystal, and as a result, highly pure crystals are obtained.
その反面、■族元素金属と塩化水素の反応が必要であり
、また、１塩化物の発生は塩化水素の供給を停止しても
、■族金属ソースに溶け込んだαが徐々に飛び出すため
すぐに止まらず、ＡＬＥの交互供給のプロセスをガスの
切り換えだけで行うことができない。このために、複雑
な基板結晶の移動が必要になるという欠点を有していた
。On the other hand, it is necessary to react the group III element metal with hydrogen chloride, and even if the supply of hydrogen chloride is stopped, the generation of monochloride is immediate because α dissolved in the group III metal source gradually jumps out. The process of alternate supply of ALE cannot be performed simply by switching the gas. For this reason, there is a drawback that a complicated movement of the substrate crystal is required.
一方、Ｔ｝ＩＧ − Ａｓ｝１３ − ８２系によるＧ
ａＡｓ ＡＬＥ装置の概略構成図を第３図に示す。この
方法では■族有機原料３１は、恒温槽３２で制御ざれた
蒸気圧を利用して水素キャリアガスで反応管３３に輸送
されるために、反応管３３内にはハロゲン輸送法のよう
なソース領域を必要としない。ＡＬＥ成長は、バルブ３
７ａ−ｇを利用して、ＴＭＧのような■族有機原料３１
、ＡｓＨ３のようなＶ族原料ガス３５、およびパジ用の
Ｈ２ガスの切り換えだけで実坦できるという大きな特徴
を有している。On the other hand, G by T}IG-As}13-82 system
A schematic diagram of the aAs ALE device is shown in FIG. In this method, the group (III) organic raw material 31 is transported to the reaction tube 33 with a hydrogen carrier gas using the vapor pressure controlled in the constant temperature bath 32, so there is no source in the reaction tube 33, such as a halogen transport method. Does not require space. ALE growth is valve 3
Using 7a-g, group II organic raw materials such as TMG 31
, AsH3, or other V group raw material gas 35, and purge H2 gas.
ところで、この方法における問題点は、有機金属の分解
が基板結晶３４上の極めて近傍で起きるために、分解し
たハイドロカーボンが成長表面上に吸着して、その結果
、カーボンが成長結晶の中に大量に取り込まれることで
ある。このために、成長結晶は高いキャリア濃度を有す
るｐ型結晶となりやすい。そして、このカーボンの影響
を少なくするためには原料ガス流速の高速化などの成長
条件の厳密な制御が必要であった。また、原料ガス中に
含まれているＳｉのような不純物に対しては、ハロゲン
輸送法のような純化の機構が働かず、高純度結晶を得る
ためには不利であった。However, the problem with this method is that since the decomposition of the organometallic occurs very close to the substrate crystal 34, the decomposed hydrocarbons are adsorbed onto the growing surface, and as a result, a large amount of carbon is deposited inside the growing crystal. It is to be taken into account. For this reason, the grown crystal tends to be a p-type crystal with a high carrier concentration. In order to reduce the influence of carbon, it is necessary to strictly control the growth conditions, such as increasing the flow rate of the raw material gas. Further, the purification mechanism such as the halogen transport method does not work for impurities such as Si contained in the raw material gas, which is disadvantageous for obtaining high-purity crystals.
本発明は、従来のＡＬＥ法におけるこのような欠点を取
り除き、クロライドＡＬＥの高純度成長と、｝ｔｏ−Ａ
ＬＥ法の簡便な原料輸送方法の両方の特徴を兼ね備えた
、従来にない新しいＡＬＥ法による化合物半導体の気相
成長方法を提供することを目的とする。The present invention eliminates such drawbacks in the conventional ALE method, and achieves high purity growth of chloride ALE and }to-ALE.
The object of the present invention is to provide a method for vapor phase growth of compound semiconductors using a new and unprecedented ALE method, which combines the features of the LE method as a simple material transportation method.
［課題を解決するための手段］
本発明は、■族元素原料と■族元素原料を交互に反応管
内の基板結晶領域に供給して基板結晶上にエピタキシャ
ル結晶成長を行う化合物半導体の気相成長方法において
、■族元素を含有する有機金属化合物を■族元素原料と
して用い、該有機金属化合物と塩化水素とを反応ざぜて
■族元素の塩化物とした後、該塩化物を基板結晶領域に
輸送する工程と、前記基板結晶領域を水素キャリアガス
で置換する工程と、Ｖ族元索原料を前記基板結晶領域に
輸送する工程と、前記基板結晶領域を水素キャリアガス
で置換する工程とを順次繰り返してなることを特徴とす
る化合物半導体の気相成長方法である。[Means for Solving the Problems] The present invention provides a method for vapor phase growth of a compound semiconductor in which a group (III) element raw material and a group (III) element raw material are alternately supplied to a substrate crystal region in a reaction tube to grow epitaxial crystals on a substrate crystal. In the method, an organometallic compound containing a group (III) element is used as a group (III) element raw material, the organometallic compound and hydrogen chloride are reacted to form a chloride of the group (III) element, and then the chloride is applied to a crystal region of a substrate. A step of transporting, a step of substituting the substrate crystal region with a hydrogen carrier gas, a step of transporting the V group element base material to the substrate crystal region, and a step of substituting the substrate crystal region with a hydrogen carrier gas are sequentially carried out. This is a method for vapor phase growth of compound semiconductors characterized by repeated growth.
なお、本発明の方法によって成長できる化合物半導体と
しては、ＧａＡｓ， ＩｎＰ等の他、゜３元，４元を
含むＩＩＩ−Ｖ族化合物半導体が挙げられ、ざらに、Ｉ
Ｉ−Ｖｌ族化合物半導体の成長にも応用することができ
る。Compound semiconductors that can be grown by the method of the present invention include GaAs, InP, etc., as well as III-V compound semiconductors containing tertiary and quaternary elements;
It can also be applied to the growth of I-Vl group compound semiconductors.
［作用］
第１図は本発明の方法の実施に用いられる装置の概略構
成図で、ここでは■族有機原料１１としてＴＭＧを用い
たＧａＡｓ ＡＬＥ成長を例にとって本発明の作用につ
いて説明する。[Function] FIG. 1 is a schematic diagram of an apparatus used to carry out the method of the present invention.Here, the function of the present invention will be explained by taking as an example GaAs ALE growth using TMG as the group Ⅰ organic material 11.
ＴＭＧは塩化水素１２と共に反応管１３に導入ざれる。TMG is introduced into the reaction tube 13 together with hydrogen chloride 12.
反応管１３は抵抗加熱炉１４により全体が加熱ざれる。The entire reaction tube 13 is heated by a resistance heating furnace 14.
１ＦＩＧは反応管中ですぐに（１）式のようにＧａとメ
タンに分解する。1FIG immediately decomposes into Ga and methane in the reaction tube as shown in equation (1).
Ｇａ （ＣＨ３ ） ３ ＋ ３／２Ｈ２ ←Ｇａ＋
３ＣＨ４ ・（１）ここで分解したＧａは同時に供給さ
れたＨＣ１と反応してＧａｃＩｌを生じる。Ga (CH3) 3 + 3/2H2 ←Ga+
3CH4 ・(1) Ga decomposed here reacts with HC1 supplied at the same time to generate GacIl.
Ｇａ＋ＨＣＪ ＧａＣｊ！＋１／２８２
＝・（２）これが、水素キャリアガスで下流の基板
結晶１５領域に運ばれ、基板結晶１５上にＧａαが吸着
する。Ga+HCJ GaCj! +1/282
=・(2) This is carried by the hydrogen carrier gas to the downstream region of the substrate crystal 15, and Gaα is adsorbed onto the substrate crystal 15.
ここで、ＴＨＧと塩化水素とはほぼ同モル数だけ供給す
る。もし、Ｔ｝ＩＧのほうが多ければ、上流側でＧａの
析出が生じ、逆に塩化水素が多ければ余分な塩化水素が
下流の基板結晶１５領域に輸送され、Ｇａαの吸着阻害
を引き起こす。Here, THG and hydrogen chloride are supplied in approximately the same number of moles. If there is more T}IG, Ga will precipitate on the upstream side, and if there is more hydrogen chloride, excess hydrogen chloride will be transported downstream to the substrate crystal 15 region, causing inhibition of Gaα adsorption.
本発明の方法では、バルブ１７ａ−ｉの操作により原料
の反応管への供給を停止すれば、ＧａＣｉのような塩化
物の基板領域への輸送を止めることができる。そこで、
ＡＬＥ成長プロセスを進めるためには、■族元素の塩化
物を基板結晶上に吸着させた後、■族有機金属とＨαガ
スの供給を停止し、次に、Ｈ２ガスだけで反応管中の余
分な塩化物のパジを行う。続いて、■族原料ガス１６の
ＡｓＨ３を反応管中に供給し、基板結晶に吸着していた
ＧａＣｌ２との反応によりＧａＡｓ層を成長させる。こ
の後、再び■２ガスのみで基板結晶領域から余分なＡＳ
Ｈ３をパージする。ＡＬＥ成長はこれらのステップを繰
り返しながら進む。In the method of the present invention, if the supply of raw materials to the reaction tube is stopped by operating the valves 17a-i, the transport of chlorides such as GaCi to the substrate region can be stopped. Therefore,
In order to proceed with the ALE growth process, after adsorbing the chloride of the group III element onto the substrate crystal, the supply of the group III organic metal and Hα gas is stopped, and then the excess in the reaction tube is removed using only H2 gas. Do a chloride purge. Subsequently, AsH3, which is the Group 1 raw material gas 16, is supplied into the reaction tube, and a GaAs layer is grown by reaction with GaCl2 adsorbed on the substrate crystal. After this, again ■ Excess AS is removed from the substrate crystal region using only 2 gases.
Purge H3. ALE growth progresses by repeating these steps.
このように、本発明により、■族有機原料と塩化水素を
用いることによって、■族元素の塩化物を吸着物質とし
ながら、ガスの切り換えだけでＡＬＥプロセスを実現す
ることができる。同時に、クロライドＡＬＥ法における
■族金属ソース枯渇の問題を避けることができ、また■
族有機原料の分解反応（反応式（１））、および塩化水
素との反応（反応式（２））は６００〜７００℃程度の
温度でも充分に進行するため、クロライドＡＬＥ法のよ
うに■族ソース領域を高温に上げる必要性もない。また
、Ｔ｝ＩＱなどの有機原料は抵抗加熱方式のために充分
に分解し、炭化水素はほとんどメタンやエタンとなり高
次のハイドロカーボンの発生は極めて低い。As described above, according to the present invention, by using the group (I) organic raw material and hydrogen chloride, it is possible to realize the ALE process by simply switching the gas while using the chloride of the group (I) element as the adsorbent. At the same time, the problem of group III metal source depletion in the chloride ALE method can be avoided, and
The decomposition reaction of group organic raw materials (reaction formula (1)) and the reaction with hydrogen chloride (reaction formula (2)) proceed satisfactorily even at temperatures of about 600 to 700°C. There is also no need to raise the source region to high temperatures. In addition, organic raw materials such as T}IQ are sufficiently decomposed due to the resistance heating method, and most of the hydrocarbons become methane and ethane, and the generation of higher-order hydrocarbons is extremely low.
また、基板表面上に吸着しやすいラジカルも、下流まで
に輸送される間に安定なものに変わり、８０−ＡＬＥ法
で見られるような成長結晶へのカーボン汚染は極めて小
さい。この結果、高純度エピタキシャル結晶を得ること
ができる。In addition, radicals that are easily adsorbed onto the substrate surface are converted into stable ones while being transported downstream, and carbon contamination of the growing crystal as seen in the 80-ALE method is extremely small. As a result, a highly pure epitaxial crystal can be obtained.
［実施例コ
次に本発明の実施例について図面を参照して詳細に説明
する。[Embodiments] Next, embodiments of the present invention will be described in detail with reference to the drawings.
実施例１
ここでは、ＧａＡｓ ＡＬＥに本発明を適用した実施例
について、第１図を用いて説明する。■族有機金属原料
ＨにはＴＨＧ， Ｖ族原料１６にはＡＳＨ３を用いた。Example 1 Here, an example in which the present invention is applied to GaAs ALE will be described with reference to FIG. THG was used as the group (2) organic metal raw material H, and ASH3 was used as the group V raw material 16.
反応管１３は横型の石英管で、抵抗加熱炉１４により、
■族有機原料と塩化水素の混合領域は６５０゜Ｃに、基
板結晶１５領域は４５０℃にｈｌ熱される。The reaction tube 13 is a horizontal quartz tube, and is heated by a resistance heating furnace 14.
The area where the group (Ⅰ) organic raw material and hydrogen chloride are mixed is heated to 650°C, and the substrate crystal 15 area is heated to 450°C.
ＴＭＧの供給量は、恒温槽１８による原料容器の温度制
御と水素キャリアガス流量により制御し、１分間に１
ＸＩＯ−４ ｍｏｌとした。一方、塩化水素１２は流量
をマスフローコントローラ１９ｃにより制御し、■族有
機原料１１と同じ＜ １ ｘ １０−４ ＩＩｌｏｔ／
ｍｉｎで供給した。両者を反応管１３内の高温部で混合
し、ＧａＣｆｌとしてＨ２キャリアガスにより基板結晶
１５＠滅に輸送する。ＡｓＨ３は導入管２０より５Ｘ１
０−４ｍｏｌ／ｍｉｎの割合で反応管１３に導入ざれる
。基板結晶１５領域における全流量は７ １２ ／ｍｉ
ｎである。The supply amount of TMG is controlled by the temperature control of the raw material container by the constant temperature bath 18 and the hydrogen carrier gas flow rate, and is controlled at a rate of 1 per minute.
It was set as XIO-4 mol. On the other hand, the flow rate of the hydrogen chloride 12 is controlled by the mass flow controller 19c, and the flow rate is the same as the group II organic raw material 11 < 1 x 10-4 IIlot/
It was supplied at min. Both are mixed in a high temperature section within the reaction tube 13 and transported as GaCfl to the substrate crystal 15 by H2 carrier gas. AsH3 is 5X1 from the introduction pipe 20
It is introduced into the reaction tube 13 at a rate of 0-4 mol/min. The total flow rate in the substrate crystal 15 region is 7 12 /mi
It is n.
基板結晶１５としては、ＧａＡＳ（１００）高抵抗結晶
を用いた。結晶基板１５を反応管１３にセットしたのち
、ＡｓＨ３を供給しながら昇温し、所定の温度に達した
ところで、ＡＬＥプロセスを開始する。それぞれのステ
ップの時間は次の通りとした。As the substrate crystal 15, a GaAS (100) high resistance crystal was used. After setting the crystal substrate 15 in the reaction tube 13, the temperature is raised while supplying AsH3, and when a predetermined temperature is reached, the ALE process is started. The time for each step was as follows.
ＴＭＧ＋ ＨＣｉ供給 ：１秒
Ｈ２によるパージ：３秒
ＡｓＨ３供給 ：２秒
１１２によるパージ：３秒
このように９秒を１サイクルとして１０００サイクルの
ＧａＡｓ成長を行った。１サイクルに換算した成長速度
は２． ８Ａ ７サイクルであり、単分子成長が実現ざ
れていることがわかった。また、４．２Ｋでホトルミネ
ッセンス測定を行った結果、フリーエキシトンピークが
明瞭に観測ざれ、カーボンに起因するアクセプターレベ
ルを介した発光はきわめて弱いものであった。TMG + HCi supply: 1 second H2 purge: 3 seconds AsH3 supply: 2 seconds 112 purge: 3 seconds In this way, 1000 cycles of GaAs growth were performed with 9 seconds as one cycle. The growth rate converted to one cycle is 2. 8A 7 cycles, and it was found that single molecule growth was achieved. Further, as a result of photoluminescence measurement at 4.2K, a free exciton peak was clearly observed, and the light emission via the acceptor level due to carbon was extremely weak.
実施例２
ここでは、ＩｎＰ ＡＬＥに本発明を適用した実施例に
ついて、第１図を用いて説明する。■族有機金属原料１
１には、ＴＥＩ （ ｔｒｉｅｔｈｙｌｉｎｄｉｕｍ
：Ｉｎ （Ｃ２ Ｈ５）３）、Ｖ族原料１６にはＰ
Ｉ−１３を用いた。反応管１３は横型の石英管で、抵抗
加熱炉１４により、■族有機原料１１と塩化水素１２の
混合領域は６５０’Ｃに、基板結晶１５領域は４００゜
Ｃにｈロ熱ざれる。Example 2 Here, an example in which the present invention is applied to InP ALE will be described with reference to FIG. ■Group organometallic raw material 1
1 includes TEI ( triethylindium
:In(C2H5)3), P for group V raw material 16
I-13 was used. The reaction tube 13 is a horizontal quartz tube, and a resistance heating furnace 14 heats the area where the organic material 11 and the hydrogen chloride 12 are mixed to 650°C, and the area where the substrate crystal 15 is heated to 400°C.
丁ＥＩの供給量を、恒温槽１８による原料容器の温度制
御と、水素キャリアガス流量により制御し、１分間に１
ＸＩＯ−４ ｍｏｌの割合で反応管１３に供給する。The supply amount of Ding EI is controlled by controlling the temperature of the raw material container using the constant temperature bath 18 and the flow rate of the hydrogen carrier gas, and is controlled at a rate of 1 per minute.
It is supplied to the reaction tube 13 at a ratio of XIO-4 mol.
一方、塩化水素１２は流量をマスフローコントローラ１
９ｃにより制御し、■族有機原料１１と同じ＜ １ ｘ
１０−４ ｍｏｌ／ｍｉｎで供給した。両者を反応管
１３内の高温部で混合し、ＩｎｒＵとしてＨ２キャリア
ガスにより基板結晶１５領域に輸送する。ＰＨ３は導入
管２０より５ｘｌＯ−４ ｎｏｔ／ｍｉｎの割合で反応
管１３に導入ざれる。基板結晶１５領域における全流量
は７（２ ／ｍｉｎである。On the other hand, the flow rate of hydrogen chloride 12 is controlled by the mass flow controller 1.
Controlled by 9c, same as group Ⅰ organic raw material 11 < 1 x
It was supplied at a rate of 10-4 mol/min. Both are mixed in a high temperature section within the reaction tube 13 and transported as InrU to the substrate crystal 15 region by H2 carrier gas. PH3 is introduced into the reaction tube 13 from the introduction tube 20 at a rate of 5xlO-4 not/min. The total flow rate in the substrate crystal 15 region is 7 (2 2 /min).
基板結晶１５としては、ＩｎＰ（１００）高抵抗結晶を
用いた。結晶基板１５を反応管１３にセットしたのち、
ＰＨ３を供給しながら昇温し、所定の温度に達したとこ
ろで、ＡＬＥプロセスを開始する。それぞれのステップ
の時間は次の通りとした。As the substrate crystal 15, an InP (100) high resistance crystal was used. After setting the crystal substrate 15 in the reaction tube 13,
The temperature is raised while supplying PH3, and when a predetermined temperature is reached, the ALE process is started. The time for each step was as follows.
ＴＥＩ十ＨＩＪ供給 ＝１秒
■２によるパージ：３秒
ＰＨ３供給 ＝２秒
■２によるパージ：３秒
このように９秒を１サイクルとして１０００サイクルの
ＩｎＰ成長を行った。１サイクルに換算した成長速度は
２．９人／サイクルであり、単分子成長か実現ざれてい
ることがわかった。また、４．２Ｋでホトルミネツセン
ス測定を行った結果、フリーエキシトンピークが明瞭に
観測され、カーボンに起因するアクセプターレベルを介
した発光はきわめて弱いものであった。TEI + HIJ supply = 1 second ■ Purge by 2: 3 seconds PH3 supply = 2 seconds ■ Purge by 2: 3 seconds In this way, InP growth was performed for 1000 cycles with 9 seconds as one cycle. The growth rate converted to one cycle was 2.9 people/cycle, indicating that single molecule growth was achieved. Furthermore, as a result of photoluminescence measurement at 4.2K, a free exciton peak was clearly observed, and the light emission via the acceptor level due to carbon was extremely weak.
なお、本実施例では、ＧａＡｓ， ＩｎＰについての
ＡＬＥ成長例を示したが、この他にも、３元，４元を含
む■−ｖ族化合物半導体のエピタキシャル成長、ざらに
は、ｎ − Ｖｌ族化合物半導体の成長にも本手法を適
用できることは明らかである。In addition, in this example, ALE growth examples of GaAs and InP are shown, but in addition to these, epitaxial growth of ■-V group compound semiconductors including ternary and quaternary elements, and more specifically, n-Vl group compound semiconductors are also possible. It is clear that this method can also be applied to the growth of semiconductors.
［発明の効果］
以上説明したように、本発明の方法によれば、クロライ
ドＡＬＥ法による時の高純度成長の特徴と、ＮＯ−ＡＬ
Ｅ法の簡便な成長系の特徴を両方兼ね備えたＡＬＥ成長
方法による化合物半導体の気相成長方法が達成される。[Effects of the Invention] As explained above, according to the method of the present invention, the characteristics of high purity growth when using the chloride ALE method and the
A compound semiconductor vapor phase growth method using the ALE growth method that has both the features of the simple growth system of the E method is achieved.
第１図は本発明の方法の実施に用いられる成長装置の一
例の概略構成図、第２図は従来技術におけるクロライド
ＡＬＥ装置の概略構成図、第３図は従来技術におけるＮ
Ｏ−ＡＬＥ装置の概略構成図である。
１１． ３１・・・■族有機原料 １２・・・塩化水
素（ＨＣｉ）１３． ３３・・・反応管 １４
・・・抵抗加熱炉１５， ２４． ３４・・・基板結晶
１６． ３５・・・Ｖ族原料１７ａ −ｉ ， ３
７ａ〜９・・・バルブ１８． ３２・・・恒温槽
１９ａ〜９，３６・・・マスフローコントローラ２０・
・・導入管 ２１・・・上部反応管２２・
・・Ｇａソースボート ２３・・・下部反応管２６
・・・基板ホルダの移動の軌跡
２７・・・基板ホルダFIG. 1 is a schematic block diagram of an example of a growth apparatus used to carry out the method of the present invention, FIG. 2 is a schematic block diagram of a chloride ALE apparatus in the prior art, and FIG.
FIG. 1 is a schematic configuration diagram of an O-ALE device. 11. 31...Group organic raw material 12...Hydrogen chloride (HCi)13. 33...Reaction tube 14
...Resistance heating furnace 15, 24. 34...Substrate crystal 16. 35... Group V raw material 17a-i, 3
7a-9...Valve 18. 32... Constant temperature chamber 19a-9, 36... Mass flow controller 20.
...Introduction tube 21...Upper reaction tube 22.
...Ga source boat 23...Lower reaction tube 26
...Trajectory of substrate holder movement 27...Substrate holder
Claims (1)
の基板結晶領域に供給して基板結晶上にエピタキシャル
結晶成長を行う化合物半導体の気相成長方法において、
III族元素を含有する有機金属化合物をIII族元素原料と
して用い、該有機金属化合物と塩化水素とを反応させて
III族元素の塩化物とした後、該塩化物を基板結晶領域
に輸送する工程と、前記基板結晶領域を水素キャリアガ
スで置換する工程と、Ｖ族元素原料を前記基板結晶領域
に輸送する工程と、前記基板結晶領域を水素キャリアガ
スで置換する工程とを順次繰り返してなることを特徴と
する化合物半導体の気相成長方法。(1) In a compound semiconductor vapor phase growth method in which a group III element raw material and a group V element raw material are alternately supplied to a substrate crystal region in a reaction tube to grow epitaxial crystals on a substrate crystal,
An organometallic compound containing a group III element is used as a group III element raw material, and the organometallic compound and hydrogen chloride are reacted.
After converting the group III element into a chloride, a step of transporting the chloride to the crystalline region of the substrate, a step of replacing the crystalline region of the substrate with a hydrogen carrier gas, and a step of transporting the group V element raw material to the crystalline region of the substrate. A method for vapor phase growth of a compound semiconductor, comprising sequentially repeating the steps of: and substituting the substrate crystal region with a hydrogen carrier gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4991189A JPH02230722A (en) | 1989-03-03 | 1989-03-03 | Vapor growth method of compound semiconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4991189A JPH02230722A (en) | 1989-03-03 | 1989-03-03 | Vapor growth method of compound semiconductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02230722A true JPH02230722A (en) | 1990-09-13 |
Family
ID=12844197
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4991189A Pending JPH02230722A (en) | 1989-03-03 | 1989-03-03 | Vapor growth method of compound semiconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02230722A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1167569A1 (en) * | 2000-06-24 | 2002-01-02 | IPS Limited | Apparatus and method for depositing thin film on wafer using atomic layer deposition |
| US7732325B2 (en) | 2002-01-26 | 2010-06-08 | Applied Materials, Inc. | Plasma-enhanced cyclic layer deposition process for barrier layers |
| US7781326B2 (en) | 2001-02-02 | 2010-08-24 | Applied Materials, Inc. | Formation of a tantalum-nitride layer |
| US10280509B2 (en) | 2001-07-16 | 2019-05-07 | Applied Materials, Inc. | Lid assembly for a processing system to facilitate sequential deposition techniques |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63182299A (en) * | 1987-01-21 | 1988-07-27 | Nec Corp | Vapor growth method for iii-v compound semiconductor |
-
1989
- 1989-03-03 JP JP4991189A patent/JPH02230722A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63182299A (en) * | 1987-01-21 | 1988-07-27 | Nec Corp | Vapor growth method for iii-v compound semiconductor |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1167569A1 (en) * | 2000-06-24 | 2002-01-02 | IPS Limited | Apparatus and method for depositing thin film on wafer using atomic layer deposition |
| US6579372B2 (en) | 2000-06-24 | 2003-06-17 | Ips, Ltd. | Apparatus and method for depositing thin film on wafer using atomic layer deposition |
| US7781326B2 (en) | 2001-02-02 | 2010-08-24 | Applied Materials, Inc. | Formation of a tantalum-nitride layer |
| US10280509B2 (en) | 2001-07-16 | 2019-05-07 | Applied Materials, Inc. | Lid assembly for a processing system to facilitate sequential deposition techniques |
| US7732325B2 (en) | 2002-01-26 | 2010-06-08 | Applied Materials, Inc. | Plasma-enhanced cyclic layer deposition process for barrier layers |
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