JPH0620047B2 - (III)-(V) Group compound semiconductor atomic layer epitaxial growth method - Google Patents
(III)-(V) Group compound semiconductor atomic layer epitaxial growth methodInfo
- Publication number
- JPH0620047B2 JPH0620047B2 JP5517387A JP5517387A JPH0620047B2 JP H0620047 B2 JPH0620047 B2 JP H0620047B2 JP 5517387 A JP5517387 A JP 5517387A JP 5517387 A JP5517387 A JP 5517387A JP H0620047 B2 JPH0620047 B2 JP H0620047B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- growth
- iii
- epitaxial growth
- compound semiconductor
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 38
- 150000001875 compounds Chemical class 0.000 title claims description 14
- 239000004065 semiconductor Substances 0.000 title claims description 13
- 239000013078 crystal Substances 0.000 claims description 38
- 239000000758 substrate Substances 0.000 claims description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- 150000004678 hydrides Chemical class 0.000 claims description 11
- 229910021476 group 6 element Inorganic materials 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 229910021478 group 5 element Inorganic materials 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000001947 vapour-phase growth Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 28
- 239000007789 gas Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 6
- 238000011144 upstream manufacturing Methods 0.000 description 6
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 5
- 238000003877 atomic layer epitaxy Methods 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 229910000673 Indium arsenide Inorganic materials 0.000 description 3
- 229910021617 Indium monochloride Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 3
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- 238000003486 chemical etching Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002052 molecular layer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、原子単位で完全に平坦な成長面を有するIII
−Ｖ族化合物半導体の原子層エピタキシャル層の成長方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention has a completely flat growth surface in atomic units. III.
The present invention relates to a method for growing an atomic layer epitaxial layer of a group V compound semiconductor.
従来のＧａＡｓ等の化合物半導体の薄膜エピタキシャル
層の成長方法としては、構成元素の塩化物，水素化物，
あるいは有機金属化合物のガス状原料を用いる気相エピ
タキシャル成長法（ＶＰＥ法）、または、高真空中で構
成元素をビーム化し、基板結晶上に照射して成長を行う
分子線エピタキシャル成長法（ＭＢＥ法）などが用いら
れてきた。ところで、これらの成長法では、単分子・原
子層（数Å程度）の成長膜厚の制御となると、流量，圧
力，時間といった要因を極めて精密に制御しなければな
らない。そこで、これらを解決する優れた手法として、
化合物半導体の構成元素、あるいは、その元素を含むガ
スを交互に供給して一原子・分子層ずつ吸着させ全体と
して所望の化合物半導体を成長させる原子層エピタキシ
ャル成長方法（ＡＬＥ法）が提案された〔ツォモ・スン
トラ (T.Suntola)，第16回固体素子・材料コンファレ
ンス(Extended Abstract of the 16th Conference on S
olid State Device and Materials)，Kobe，1984，pp.6
47-650〕。この手法は本発明者等により、III−Ｖ族化
合物半導体の成長にも適用された。この方法によると、
膜厚制御のためには、従来の成長速度を制御する方法と
は異なり、例えば、ＧａＣｌとＡｓＨ３を原料とするＧ
ａＡｓ ＡＬＥ法では、ＧａＣｌの吸着回数のみを制御
することになる。しかも、広い成長温度，流量範囲にお
いて、単分子層単位の成長が可能であり、これによって
膜厚の制御技術は格段に向上した（碓井（A.Usui）他、
ジャパニーズ ジャーナル オブ アプライド フィジ
ックス(Japanese Journal of Applied Physics),vol.2
5,no.3,1976,PP.L212-214〕。As a conventional method for growing a thin film epitaxial layer of a compound semiconductor such as GaAs, there are chloride, hydride,
Alternatively, a vapor phase epitaxial growth method (VPE method) using a gaseous raw material of an organometallic compound, or a molecular beam epitaxial growth method (MBE method) in which a constituent element is converted into a beam in a high vacuum and irradiated on a substrate crystal for growth. Has been used. By the way, in these growth methods, when controlling the growth film thickness of a monomolecular / atomic layer (about several Å), factors such as flow rate, pressure, and time must be controlled extremely precisely. So, as an excellent method to solve these,
An atomic layer epitaxial growth method (ALE method) has been proposed in which a constituent element of a compound semiconductor or a gas containing the element is alternately supplied to adsorb one atom / molecular layer at a time to grow a desired compound semiconductor as a whole (ALE method).・ T.Suntola, 16th Solid State Device and Materials Conference (Extended Abstract of the 16th Conference on S
Solid State Device and Materials), Kobe, 1984, pp.6
47-650]. This method was also applied by the present inventors to the growth of III-V group compound semiconductors. According to this method,
For controlling the film thickness, unlike the conventional method of controlling the growth rate, for example, G using GaCl and AsH 3 as raw materials is used.
In the aAs ALE method, only the number of times GaCl is adsorbed is controlled. Moreover, it is possible to grow in a single molecular layer unit over a wide growth temperature and flow rate range, which has significantly improved the film thickness control technology (A. Usui et al.,
Japanese Journal of Applied Physics, vol.2
5, no. 3, 1976, PP.L212-214].
ところが、このIII族元素の塩化物と、Ｖ族元素、ある
いはその水素化物とを交互に供給するIII−Ｖ族化合物
半導体の原子層エピタキシャル成長技術にも、解決すべ
き幾つかの問題点がある。本発明が解決しようとした問
題点あそのなかでも極めて重要なもので成長面の平坦性
に関するものである。即ち、この成長手法においては、
III族元素の塩化物の基板結晶上への吸着は基板表面の
凹凸をそのまま受け継ぎ、その後Ｖ族元素を供給し、Ｇ
ａ−Ａｓボンドを形成しても、その表面拡散が成長温度
（500℃付近）程度では極めて小さく成長面の平坦化に
は殆ど寄与しない。従って、成長終了後においても成長
面は基板表面の形状をそのまま受け継いでいると考えら
れる。このような成長モードは単に厚い膜を成長させる
時にはあまり問題にならないが、規則性混晶や超格子を
成長させた場合その特徴を十分発揮させることができな
い。ところで、基板結晶の凹凸の軽減には、通常のＶＰ
ＥやＭＢＥ法でもlayer-ba-layer成長に近い条件でエピ
タキシャル成長させることが有効とされている。しかし
ながら、この方法によっても原子オーダで完全に平坦な
成長面を有するエピタキシャル成長面を得ることは極め
て困難であった。However, there are some problems to be solved in the atomic layer epitaxial growth technique for III-V group compound semiconductors in which the group III element chloride and the group V element or its hydride are alternately supplied. Among the problems that the present invention has tried to solve, it is extremely important and is related to the flatness of the growth surface. That is, in this growth method,
Adsorption of the chloride of the group III element on the substrate crystal inherits the unevenness of the substrate surface as it is, and then supplies the group V element and G
Even if an a-As bond is formed, its surface diffusion is extremely small at a growth temperature (around 500 ° C.), and it hardly contributes to flattening the growth surface. Therefore, it is considered that the growth surface inherits the shape of the substrate surface even after the growth is completed. Such a growth mode does not pose a problem when merely growing a thick film, but when a regular mixed crystal or a superlattice is grown, its characteristics cannot be sufficiently exhibited. By the way, in order to reduce the unevenness of the substrate crystal, a normal VP is used.
Even in the E and MBE methods, it is effective to grow epitaxially under conditions close to layer-ba-layer growth. However, even by this method, it is extremely difficult to obtain an epitaxial growth surface having a growth surface that is completely flat on the atomic order.
本発明の目的は、上記従来技術のかかる欠点を除去し、
原子オーダで完全に平坦な成長面を有するIII−Ｖ族化
合物半導体の原子層エピタキシャル層の成長方法を提供
しようとするものである。The object of the present invention is to eliminate the above-mentioned drawbacks of the prior art,
An object of the present invention is to provide a method for growing an atomic layer epitaxial layer of a III-V group compound semiconductor having a completely flat growth surface in atomic order.
本発明は、III−Ｖ族化合物半導体の原子層エピタキシ
ャル成長方法において、先ず、基板結晶上に通常のハロ
ゲン輸送法による気相成長法を用いてバッファ層を形成
した後、これに引き続いてIII族元素の塩化物を供給し
て吸着層を形成した後、気相中のIII族元素の塩化物を
排出し、次にVI族元素、あるいはその水素化物を基板結
晶上に一定時間供給するプロセスを少なくとも一回以上
繰り返し、その後Ｖ族元素、あるいはその水素化物とII
I族元素の塩化物とを交互に供給することによりエピタ
キシャル成長を行うことを特徴とする。The present invention relates to an atomic layer epitaxial growth method for a III-V group compound semiconductor, in which a buffer layer is first formed on a substrate crystal by a vapor phase growth method using a normal halogen transport method, and subsequently, a Group III element is formed. At least after supplying the chloride of the group III to form an adsorption layer, discharging the chloride of the group III element in the vapor phase, and then supplying the group VI element or its hydride onto the substrate crystal for a certain period of time. Repeated once or more, and then group V element or its hydride and II
It is characterized in that epitaxial growth is performed by alternately supplying Group I element chlorides.
前述したように基板結晶の凹凸の軽減には通常のＶＰＥ
やＭＢＥ法でlayer-by-layer成長に近い条件で、ある程
度の厚さにエピタキシャル成長させることが有効な方法
として知られている。本発明では、先ずこの方法によっ
てある程度平坦な成長面を形成する。次に、III族元素
の塩化物のみを成長表面に供給すると、これらは成長表
面の凹凸をそのまま受け継ぎ吸着すると考えられる。こ
の後、気相中のIII族元素の塩化物を排出し、新たにVI
族元素、あるいはその水素化物を基板結晶上に一定時間
供給することにより、これらは吸着したIII族元素の塩
化物の塩素をはずしてIII族元素と結合する。ところ
が、成長温度が高いとVI族元素は再び気相中に飛び出
し、成長表面にはIII族元素のダングリングボンド（dan
gling bond）が残る。ところで、成長表面は原子オーダ
で平坦ではないために、VI族元素に対して結合している
ボンドの数が異なり、成長温度を適当に選ぶことによっ
て凹凸の窪みに入ったVI族元素はそのままで、最上部の
表面上のVI族元素だけを外すことが可能である。この
後、表面を再びIII族元素の塩化物をさらすと、VI族元
素の上には吸着するが、III族元素上の吸着は極めて弱
くなり、容易に気相中に飛び出す。そこで再び表面にVI
族元素、あるいはその水素化物を供給すると上記反応が
再現する。このプロセスを繰り返すことにより、凹んだ
部分が次第に埋められ、ついには原子オーダで平坦な表
面が得られる。これら一連の反応は、原理からいって平
坦な表面が得られた段階で自動的に止まる自己停止機能
を有しているのが特徴の一つである。As mentioned above, normal VPE is used to reduce the unevenness of the substrate crystal.
Known as an effective method is to epitaxially grow to a certain thickness under conditions similar to layer-by-layer growth by the MBE method or the MBE method. In the present invention, a growth surface that is somewhat flat is first formed by this method. Next, if only the chloride of the group III element is supplied to the growth surface, it is considered that these inherit and adsorb the irregularities on the growth surface as they are. After this, the chloride of the group III element in the gas phase is discharged and a new VI is added.
By supplying the group element or its hydride onto the substrate crystal for a certain period of time, the chlorine of the adsorbed group III element chloride is removed to bond with the group III element. However, when the growth temperature is high, the group VI element jumps out into the vapor phase again, and a dangling bond (dan group bond) of the group III element (dan) is formed on the growth surface.
gling bond) remains. By the way, since the growth surface is not flat in atomic order, the number of bonds bonded to the group VI element is different, and by appropriately selecting the growth temperature, the group VI element that entered the concave and convex portions remains as it is. It is possible to remove only the group VI element on the top surface. After that, when the surface is again exposed to the chloride of the group III element, it is adsorbed on the group VI element, but the adsorption on the group III element becomes extremely weak and easily jumps out into the gas phase. So again on the surface VI
When the group element or its hydride is supplied, the above reaction is reproduced. By repeating this process, the recesses are gradually filled, and finally a flat surface of atomic order is obtained. One of the features of this series of reactions is that, in principle, it has a self-stop function that automatically stops when a flat surface is obtained.
次に、本発明を実施例に基づき具体的に説明する。Next, the present invention will be specifically described based on Examples.
実施例１ 本実施例では、ＩｎＰ基板結晶に550℃で原子層エピタ
キシャル成長法により、ＧａＡｓ／ＩｎＡｓ規則性混晶
を成長した場合について述べる。成長装置の概略を第１
図に示した。反応室１の上流にＧａソース２、反応室３
の上流にＩｎソース４を置き、それらの上流から導入パ
イプ５，６を経てＨ２キャリアガスと共にＨＣｌガスを
供給する。この結果、ＧａＣｌおよびＩｎＣｌが生成さ
れ下流に運ばれる。一方、これらの反応室１，３にはＨ
Ｃｌ導入パイプ５，６とは別にＡｓＨ３あるいはＰＨ３
を導入するためのハイドライドガス導入パイプ７，８が
ある。また、反応室９には導入パイプ10からＰＨ3,Ａｓ
Ｈ３あるいはＨ２ＳｅをＨ２キャリアガスと共に供給す
る。基板結晶11としてはＩｎＰ(100) を用いた。反応室
の温度は抵抗加熱により制御し、III族金属ソース部は8
00 ℃、基板結晶部550℃とした。ガス流量条件は次の通
りである。Example 1 In this example, a case where a GaAs / InAs ordered mixed crystal is grown on an InP substrate crystal by an atomic layer epitaxial growth method at 550 ° C. will be described. First outline of growth equipment
As shown in the figure. A Ga source 2 and a reaction chamber 3 are provided upstream of the reaction chamber 1.
In source 4 is placed on the upstream side of, and HCl gas is supplied together with H 2 carrier gas from the upstream through the introduction pipes 5 and 6. As a result, GaCl and InCl are produced and carried downstream. On the other hand, in these reaction chambers 1 and 3, H
AsH 3 or PH 3 separately from the Cl introduction pipes 5 and 6.
There are hydride gas introduction pipes 7 and 8 for introducing. In addition, PH 3 and As are introduced from the introduction pipe 10 into the reaction chamber 9.
H 3 or H 2 Se is supplied together with the H 2 carrier gas. InP (100) was used as the substrate crystal 11. The temperature of the reaction chamber is controlled by resistance heating, and the group III metal source is
The temperature was set to 00 ° C and the substrate crystal part was set to 550 ° C. The gas flow rate conditions are as follows.
ＨＣｌ（Ｇａ） 10 cc/min ＨＣｌ（Ｉｎ） 10 cc/min ＡｓＨ３ 10 cc/min ＰＨ３ 10 cc/min Ｈ2Ｓｅ 10 cc/min 全流量（各反応室に対して） 5000 cc/min 成長に際しては、ケミカルエッチングを行った半絶縁性
基板結晶11を先ず反応室９に置き、ＰＨ３気流中で成長
温度まで昇温した。成長温度に達したところで反応室３
にＨＣｌおよびＰＨ３を供給し、一定時間後基板結晶11
を反応室３に移動した。そこでＩｎＰバッファ層を約１
μｍ成長させた後、基板結晶11を再び反応室９に戻し
た。そこで反応室３のＰＨ３の供給を停止し、ＩｎＣｌ
だけの雰囲気とした後基板結晶11を移動して５秒間Ｉｎ
Ｃｌにさらし、吸着させた後、基板結晶11を反応室９に
戻した。そして、表面を５秒間Ｈ2Ｓｅ雰囲気にさらし
た。その後再度基板結晶11を反応室３に移動し、このサ
イクルを10回繰り返した。HCl (Ga) 10 cc / min HCl (In) 10 cc / min AsH 3 10 cc / min PH 3 10 cc / min H 2 Se 10 cc / min Total flow rate (for each reaction chamber) 5000 cc / min Growth At that time, the semi-insulating substrate crystal 11 subjected to chemical etching was first placed in the reaction chamber 9 and heated to the growth temperature in a PH 3 gas flow. Reaction chamber 3 when growth temperature is reached
HCl and PH 3 are supplied to the substrate, and after a certain time, the substrate crystal 11
Was moved to reaction chamber 3. Therefore, the InP buffer layer should be about 1
After the growth of μm, the substrate crystal 11 was returned to the reaction chamber 9. Therefore, the supply of PH 3 in the reaction chamber 3 is stopped, and InCl
After setting the atmosphere for 10 minutes, the substrate crystal 11 is moved and
After being exposed to Cl for adsorption, the substrate crystal 11 was returned to the reaction chamber 9. Then, the surface was exposed to an H 2 Se atmosphere for 5 seconds. After that, the substrate crystal 11 was again moved to the reaction chamber 3, and this cycle was repeated 10 times.
このプロセスが終了した後、原子層エピタキシャル成長
法により、ＩｎＣｌ−ＡｓＨ3−ＧａＣｌ−ＡｓＨ３の
順に基板結晶11の移動を繰り返し、先ず高抵抗のＧａＡ
ｓ／ＩｎＡｓ規則性混晶を成長させ、次にノンドープの
ＧａＡｓ／ＩｎＡｓ規則性混晶を成長させた。After this process is completed, the substrate crystal 11 is repeatedly moved in the order of InCl—AsH 3 —GaCl—AsH 3 by the atomic layer epitaxial growth method, and first, the high resistance GaA is formed.
An s / InAs ordered mixed crystal was grown, and then a non-doped GaAs / InAs ordered mixed crystal was grown.
得られた結晶のホール測定を行った結果、77Ｋにおける
移動度して105cm2/V・sec 台（キャリア濃度：〜1015cm
-3）がコンスタントに得られ、本発明を適用しない場合
の値、104cm/V・sec 台（キャリア濃度：1015cm-3）と
比較してその有効性が明らかとなった。As a result of hole measurement of the obtained crystal, the mobility at 77 K was 10 5 cm 2 / V · sec (carrier concentration: up to 10 15 cm
-3 ) was constantly obtained, and its effectiveness was clarified as compared with the value when the present invention is not applied, which is in the order of 10 4 cm / V · sec (carrier concentration: 10 15 cm -3 ).
実施例２ 本実施例では、ＧａＡｓ基板結晶に550℃で原子層エピ
タキシャル成長法により、ＩｎＰを成長した場合につい
て述べる。成長装置および成長条件は実施例１で用いた
ものと同じである。反応室１の上流にＧａソース２、反
応室３の上流にＩｎソース４を置き、それらの上流から
導入パイプ５６を経てＨ２キャリアガスと共にＨＣｌガ
スを供給する。この結果、ＧａＣｌおよびＩｎＣｌが生
成され下流に運ばれる。また、反応室９には導入パイプ
10からＡｓＨ３あるいはＨ２ＳｅをＨ２キャリアガスと
共に供給する。基板結晶11としてはＧａＡｓ(100) を用
いた。反応室の温度は抵抗加熱により制御し、III族金
属ソース部は800℃、基板結晶部は550℃とした。ガス流
量条件は次の通りである。Example 2 In this example, InP is grown on a GaAs substrate crystal at 550 ° C. by an atomic layer epitaxial growth method. The growth apparatus and growth conditions are the same as those used in Example 1. A Ga source 2 is placed upstream of the reaction chamber 1 and an In source 4 is placed upstream of the reaction chamber 3, and HCl gas is supplied together with the H 2 carrier gas from the upstream through the introduction pipe 56. As a result, GaCl and InCl are produced and carried downstream. In addition, an introduction pipe is installed in the reaction chamber 9.
AsH 3 or H 2 Se is supplied from 10 together with the H 2 carrier gas. GaAs (100) was used as the substrate crystal 11. The temperature of the reaction chamber was controlled by resistance heating, and the group III metal source part was 800 ° C and the substrate crystal part was 550 ° C. The gas flow rate conditions are as follows.
ＨＣｌ（Ｇａ） 10 cc/min ＨＣｌ（Ｉｎ） 10 cc/min ＡｓＨ３ 10 cc/min ＰＨ３ 10 cc/min Ｈ2Ｓｅ 10 cc/min 全流量（各反応室に対して） 5000 cc/min 成長に際しては、ケミカルエッチングを行った半絶縁性
基板結晶11を先ず反応室９に置き、ＡｓＨ３気流中で成
長温度まで昇温した。成長温度に達したところで反応室
１にＨＣｌおよびＡｓＨ３を供給し、一定時間後基板結
晶11を反応室１に移動した。そこでＧａＡｓバッファ層
を約１μｍ成長させた後、基板結晶11を再び反応室９に
戻した。そこで反応室１のＡｓＨ３の供給を停止し、Ｇ
ａＣｌだけの雰囲気とした後基板結晶11を移動して５秒
間ＧａＣｌにさらし、吸着させた後、基板結晶11を再び
反応室９に戻した。そして、表面を５秒間Ｈ2Ｓｅ雰囲
気にさらした。その後再度基板結晶11を反応室１に移動
し、このサイクルを10回繰り返した。HCl (Ga) 10 cc / min HCl (In) 10 cc / min AsH 3 10 cc / min PH 3 10 cc / min H 2 Se 10 cc / min Total flow rate (for each reaction chamber) 5000 cc / min Growth At this time, the semi-insulating substrate crystal 11 subjected to chemical etching was first placed in the reaction chamber 9 and heated to the growth temperature in an AsH 3 gas stream. When the growth temperature was reached, HCl and AsH 3 were supplied to the reaction chamber 1, and after a certain period of time, the substrate crystal 11 was moved to the reaction chamber 1. Then, the GaAs buffer layer was grown to about 1 μm, and the substrate crystal 11 was returned to the reaction chamber 9 again. Therefore, the supply of AsH 3 in the reaction chamber 1 was stopped, and G
After making the atmosphere of only aCl, the substrate crystal 11 was moved and exposed to GaCl for 5 seconds to be adsorbed, and then the substrate crystal 11 was returned to the reaction chamber 9 again. Then, the surface was exposed to an H 2 Se atmosphere for 5 seconds. After that, the substrate crystal 11 was again moved to the reaction chamber 1, and this cycle was repeated 10 times.
このプロセスが終了した後、原子層エピタキシャル成長
法により、ＩｎＣｌ−ＰＨ３の順に基板結晶11の移動を
繰り返し、ＩｎＰを成長させた。After this process is completed, the atomic layer epitaxy, repeating the movement of the substrate crystal 11 in the order of InCl-PH 3, was grown InP.
得られた結晶を透過電子顕微鏡により格子像を調べた結
果、基板と成長層の界面の極めて平坦な結晶が得られ
た。As a result of examining the lattice image of the obtained crystal with a transmission electron microscope, an extremely flat crystal at the interface between the substrate and the growth layer was obtained.
以上述べたように、本発明による成長方法を用いると、
原子オーダで完全に平坦な成長面を有するIII−Ｖ族化
合物半導体の原子層エピタキシャル層が得られ、その結
果、高品質の規則性混晶や超格子構造の成長が可能にな
る。なお、本発明においてはVI族元素およびその水素化
物を用いたが、同様な作用を有する他の元素あるいは化
合物に対しても適用可能であることは勿論、同様な原理
でII−VI族化合物半導体の成長にも適用できる。As described above, using the growth method according to the present invention,
It is possible to obtain an atomic layer epitaxial layer of a III-V group compound semiconductor having a completely flat growth surface in the atomic order, and as a result, it becomes possible to grow a high quality ordered mixed crystal or superlattice structure. Although the group VI element and its hydride are used in the present invention, it is of course applicable to other elements or compounds having a similar action, and, of course, a II-VI group compound semiconductor is used on the same principle. Can also be applied to the growth of.
第１図は本発明による実施例を説明するための図で、成
長装置の概略を示したものである。 １，３，９……反応室 ２……Ｇａソース ４……Ｉｎソース ５，６，19……導入パイプ ７，８……ハイドライドガス導入パイプ 11……基板結晶FIG. 1 is a view for explaining an embodiment according to the present invention, and shows an outline of a growth apparatus. 1,3,9 ... Reaction chamber 2 ... Ga source 4 ... In source 5,6,19 ... Introduction pipe 7,8 ... Hydride gas introduction pipe 11 ... Substrate crystal
Claims (1)
シャル成長方法において、先ず、基板結晶上に通常のハ
ロゲン輸送法による気相成長法を用いてバッファ層を形
成した後、これに引き続いてIII族元素の塩化物を供給
して吸着層を形成した後、気相中のIII族元素の塩化物
を排出し、次にVI族元素、アるいはその水素化物を基板
結晶上に一定時間供給するプロセスを少なくとも一回以
上繰り返し、その後Ｖ族元素、あるいはその水素化物と
III族元素の塩化物とを交互に供給することによりエピ
タキシャル成長を行うことを特徴とするIII−Ｖ族化合
物半導体の原子層エピタキシャル成長方法。1. In an atomic layer epitaxial growth method for a III-V group compound semiconductor, first, a buffer layer is formed on a substrate crystal by a vapor phase growth method by an ordinary halogen transport method, and then, a group III group is subsequently formed. After the chloride of the element is supplied to form the adsorption layer, the chloride of the group III element in the gas phase is discharged, and then the group VI element, or its hydride is supplied for a certain time on the substrate crystal. The process is repeated at least once, and then the group V element or its hydride is used.
An atomic layer epitaxial growth method for a III-V group compound semiconductor, which comprises performing epitaxial growth by alternately supplying a group III element chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5517387A JPH0620047B2 (en) | 1987-03-12 | 1987-03-12 | (III)-(V) Group compound semiconductor atomic layer epitaxial growth method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5517387A JPH0620047B2 (en) | 1987-03-12 | 1987-03-12 | (III)-(V) Group compound semiconductor atomic layer epitaxial growth method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63222421A JPS63222421A (en) | 1988-09-16 |
| JPH0620047B2 true JPH0620047B2 (en) | 1994-03-16 |
Family
ID=12991335
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5517387A Expired - Lifetime JPH0620047B2 (en) | 1987-03-12 | 1987-03-12 | (III)-(V) Group compound semiconductor atomic layer epitaxial growth method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0620047B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6620723B1 (en) | 2000-06-27 | 2003-09-16 | Applied Materials, Inc. | Formation of boride barrier layers using chemisorption techniques |
| US6551929B1 (en) | 2000-06-28 | 2003-04-22 | Applied Materials, Inc. | Bifurcated deposition process for depositing refractory metal layers employing atomic layer deposition and chemical vapor deposition techniques |
| US7101795B1 (en) | 2000-06-28 | 2006-09-05 | Applied Materials, Inc. | Method and apparatus for depositing refractory metal layers employing sequential deposition techniques to form a nucleation layer |
| US7405158B2 (en) | 2000-06-28 | 2008-07-29 | Applied Materials, Inc. | Methods for depositing tungsten layers employing atomic layer deposition techniques |
| US6765178B2 (en) | 2000-12-29 | 2004-07-20 | Applied Materials, Inc. | Chamber for uniform substrate heating |
| US6998579B2 (en) | 2000-12-29 | 2006-02-14 | Applied Materials, Inc. | Chamber for uniform substrate heating |
| US6951804B2 (en) | 2001-02-02 | 2005-10-04 | Applied Materials, Inc. | Formation of a tantalum-nitride layer |
| US6878206B2 (en) | 2001-07-16 | 2005-04-12 | Applied Materials, Inc. | Lid assembly for a processing system to facilitate sequential deposition techniques |
| US6734020B2 (en) | 2001-03-07 | 2004-05-11 | Applied Materials, Inc. | Valve control system for atomic layer deposition chamber |
| US7211144B2 (en) | 2001-07-13 | 2007-05-01 | Applied Materials, Inc. | Pulsed nucleation deposition of tungsten layers |
| US7085616B2 (en) | 2001-07-27 | 2006-08-01 | Applied Materials, Inc. | Atomic layer deposition apparatus |
| US7049226B2 (en) | 2001-09-26 | 2006-05-23 | Applied Materials, Inc. | Integration of ALD tantalum nitride for copper metallization |
| US6936906B2 (en) | 2001-09-26 | 2005-08-30 | Applied Materials, Inc. | Integration of barrier layer and seed layer |
| US6916398B2 (en) | 2001-10-26 | 2005-07-12 | Applied Materials, Inc. | Gas delivery apparatus and method for atomic layer deposition |
| US6911391B2 (en) | 2002-01-26 | 2005-06-28 | Applied Materials, Inc. | Integration of titanium and titanium nitride layers |
| US6998014B2 (en) | 2002-01-26 | 2006-02-14 | Applied Materials, Inc. | Apparatus and method for plasma assisted deposition |
| US6833161B2 (en) | 2002-02-26 | 2004-12-21 | Applied Materials, Inc. | Cyclical deposition of tungsten nitride for metal oxide gate electrode |
| US7439191B2 (en) | 2002-04-05 | 2008-10-21 | Applied Materials, Inc. | Deposition of silicon layers for active matrix liquid crystal display (AMLCD) applications |
| US7262133B2 (en) | 2003-01-07 | 2007-08-28 | Applied Materials, Inc. | Enhancement of copper line reliability using thin ALD tan film to cap the copper line |
| KR20060079144A (en) | 2003-06-18 | 2006-07-05 | 어플라이드 머티어리얼스, 인코포레이티드 | Atomic Layer Deposition of Barrier Materials |
-
1987
- 1987-03-12 JP JP5517387A patent/JPH0620047B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63222421A (en) | 1988-09-16 |
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