JPH0292894A - Method for feeding raw material in vapor-phase crystal growth process - Google Patents
Method for feeding raw material in vapor-phase crystal growth processInfo
- Publication number
- JPH0292894A JPH0292894A JP24672788A JP24672788A JPH0292894A JP H0292894 A JPH0292894 A JP H0292894A JP 24672788 A JP24672788 A JP 24672788A JP 24672788 A JP24672788 A JP 24672788A JP H0292894 A JPH0292894 A JP H0292894A
- Authority
- JP
- Japan
- Prior art keywords
- raw material
- material gas
- gas
- organometallic compound
- pressure drop
- 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
- 239000002994 raw material Substances 0.000 title claims abstract description 38
- 239000013078 crystal Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000012808 vapor phase Substances 0.000 title claims abstract description 9
- 239000012530 fluid Substances 0.000 claims abstract description 12
- 238000012544 monitoring process Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 16
- 239000012159 carrier gas Substances 0.000 abstract description 15
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 7
- 239000010935 stainless steel Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000003507 refrigerant Substances 0.000 abstract description 4
- 150000002902 organometallic compounds Chemical class 0.000 abstract 5
- 230000004888 barrier function Effects 0.000 abstract 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、水素等のキャリアガスを用いて原料の蒸気を
反応管に輸送する気相結晶成長法において、原料の供給
量をモニタしながら原料を供給する方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a vapor phase crystal growth method in which raw material vapor is transported to a reaction tube using a carrier gas such as hydrogen, while monitoring the amount of raw material supplied. Concerning a method of supplying raw materials.
■−■族、ｍ−Ｖ族の化合物半導体のエピタキシャル成
長法の一つであるＭＯＣＶＤ法（有機金属気相成長法）
では、Ｇａ、Ｉｎ、Ａｊ！等■族元素、Ｚｎ、Ｍｇ等■
族の元素の有機化合物を原料として用いる。MOCVD (metal-organic chemical vapor deposition), which is one of the epitaxial growth methods for ■-■ group and m-V group compound semiconductors.
So, Ga, In, Aj! Group elements, Zn, Mg, etc.■
Organic compounds of group elements are used as raw materials.
ｍ−ｖ族化合物半導体のＭＯＣＶＤ法成長は、一般にＶ
麹原料（ＡｓＨｓ 、ＰＨｓ ）の過剰供給状態で行わ
れ、成長速度は■族の有機金属の供給量によって決定さ
れる。MOCVD growth of m-v group compound semiconductors is generally performed at V
The process is carried out in the presence of an excess supply of koji raw materials (AsHs, PHs), and the growth rate is determined by the amount of group II organic metals supplied.
また、Ｇａ１ｌ Ｉ ｎ＋−、Ａｓ、Ｃａ、ｌ ｎ＋−
ｘ Ａｉｍ Ｐ＋−ｙ 、Ａｉｍ Ｇａ＋−１１Ａｓの
ように二種類以上の■族元素を含む結晶の■族組成比Ｘ
は、はぼ■麹原料供給量比によって決定される。従って
、有機金属の供給量の制御は、成長速度および組成を制
御するうえで、きわめて重要である。Also, Ga1l I n+-, As, Ca, l n+-
x Group ■ composition ratio X of a crystal containing two or more types of Group ■ elements such as x Aim P+-y, Aim Ga+-11As
is determined by the ratio of supply of raw material to koji. Therefore, controlling the amount of organometallic supplied is extremely important in controlling the growth rate and composition.
従来の有機金属の供給方法の一例を第２図に示す、ステ
ンレス容器（３）内に封入した有機金属（４）を恒温槽
（５）中で低温（−３０°Ｃ〜１００°Ｃ）に保ち、マ
スフローコントローラ（１）で流量制御した水素、窒素
等のキャリアガスを、液体あるいは粉状結晶となってい
る有機金属（４）中に通じ、原料の蒸気を前記キャリア
ガス中に飽和させて反応管へ導入する。なお、（２）は
圧力計、（６）は冷媒、（９）はニードルバルブである
。An example of a conventional method for supplying an organic metal is shown in Fig. 2, in which an organic metal (4) sealed in a stainless steel container (3) is heated to a low temperature (-30°C to 100°C) in a constant temperature bath (5). A carrier gas such as hydrogen or nitrogen whose flow rate is controlled by a mass flow controller (1) is passed through the organic metal (4) which is a liquid or powdered crystal, and the vapor of the raw material is saturated in the carrier gas. Introduce into reaction tube. Note that (2) is a pressure gauge, (6) is a refrigerant, and (9) is a needle valve.
原料の供給Ｉｇ （ｃｃ／ｗｉｎ）は、使用温度（恒温
槽温度）での原料の蒸気圧Ｐ （Ｔｏｒｒ） 、キャリ
アガスの流！！ｋｆ （ｃｃ／５ｉｎ） （標準状態
換算値）、ステンレス容器（３）内の圧力Ｐ、 （Ｔ
ｏｒｒ） 、飽和度ｋを用いて下式で表せる。The raw material supply Ig (cc/win) is the vapor pressure P (Torr) of the raw material at the operating temperature (thermal chamber temperature), the carrier gas flow! ! kf (cc/5in) (standard state conversion value), pressure P in the stainless steel container (3), (T
orr) and the saturation degree k can be expressed by the following formula.
有機金属の供給量を示した（１１式の中で、Ｐｏおよび
ｒはＡＰＣ（圧力制御装置）、マスフローコントローラ
等の部品が高性能化してきており比較的高度の制御が可
能である。一方Ｐは、原料の温度の関数であり、原料自
体は恒温槽中に保持されていても、キャリアガスの持ち
込みがあるために環境温度の変動の影響を受ける。The amount of organic metal supplied (in equation 11, Po and r can be controlled to a relatively high degree as parts such as APC (pressure controller) and mass flow controllers have become more sophisticated.On the other hand, P is a function of the temperature of the raw material, and even if the raw material itself is kept in a thermostatic chamber, it is affected by fluctuations in the environmental temperature because carrier gas is brought in.
また、飽和度には、はぼ１の値をとるが、原料残量の低
下に従って、徐々に低下する。これは、ＴＭＩ（トリメ
チルインジウム）のような固体（粉体）原料において顕
著である。従って、上記（１）式において、ｋＰの項を
正確に把握することは困難であり、原料供給量をモニタ
することも出来ないという問題が生じる。Further, the degree of saturation takes a value of approximately 1, but gradually decreases as the remaining amount of raw material decreases. This is remarkable in solid (powder) raw materials such as TMI (trimethylindium). Therefore, in the above equation (1), it is difficult to accurately grasp the term kP, and the problem arises that it is impossible to monitor the raw material supply amount.
〔課題を解決するための手段）
本発明は以上のような点にかんがみてなされたもので、
その目的とするところは、有機金属の供給量をモニタし
ながら有機金属を供給する気相結晶成長の原料供給方法
を提供することにあり、その要旨は、有機金属を含む原
料ガスを用いて気相結晶成長を行う気相結晶成長の原料
供給方法において、前記原料ガスの流路に流体抵抗物を
設置し、該流体抵抗物による前記ガスの圧力損失をモニ
タしながら原料ガスを供給することを特徴とする気相結
晶成長の原料供給方法である。[Means for Solving the Problems] The present invention has been made in view of the above points.
The purpose is to provide a raw material supply method for vapor phase crystal growth that supplies organic metals while monitoring the amount of organic metals supplied. In a raw material supply method for vapor phase crystal growth that performs phase crystal growth, a fluid resistor is installed in the flow path of the raw material gas, and the raw material gas is supplied while monitoring the pressure loss of the gas due to the fluid resistor. This is a characteristic material supply method for vapor phase crystal growth.
流体抵抗物による流体の圧力損失は、速度を一定にすれ
ば密度に比例する。The pressure loss of a fluid due to a fluid resistance object is proportional to the density if the velocity is constant.
上記の原料供給方法はこの性質を利用し、圧力損失から
キャリアガスに含まれる原料の割合（含有率）を知ろう
とするものである。例えば、ＴＭＩは分子量１６０の粉
状結晶であり、２５°Ｃにおける蒸気圧は約２．５Ｔｏ
ｒｒである。従って、２５℃、７６０Ｔｏｒｒのキャリ
アガスＨ！中において、ＴＭＩの体積含有率は約０．３
％であるが、ＴＭＩを含有することによって、キャリア
ガスの密度すなわち圧力損失は約２５％変化する。この
ように、わずかな有機金属の含有率の変化が大きな圧力
損失の変化をもたらすため、上記の方法によれば、既存
の圧力計で圧力損失の変化をモニタし、原料の供給状況
を確認しながら原料を供給することができる。The above raw material supply method utilizes this property to determine the ratio (content) of the raw material contained in the carrier gas from the pressure loss. For example, TMI is a powder crystal with a molecular weight of 160, and its vapor pressure at 25°C is approximately 2.5 To
It is rr. Therefore, carrier gas H at 25°C and 760 Torr! Among them, the volume content of TMI is about 0.3
%, but by including TMI, the density of the carrier gas, that is, the pressure drop changes by about 25%. In this way, a slight change in the content of organic metals causes a large change in pressure drop, so according to the above method, changes in pressure drop are monitored using existing pressure gauges to check the raw material supply status. raw materials can be supplied at the same time.
以下図面に示した実施例に基づいて本発明を説明する。 The present invention will be described below based on embodiments shown in the drawings.
第１図は本発明にかかる一実施例の説明図である。水素
などのキャリアガスはマスフローコントローラ（１′）
で流量制御された後、ステンレス容器（３′）内に封入
された有機金属（４′）に通じて有機金属を含有する。FIG. 1 is an explanatory diagram of an embodiment according to the present invention. For carrier gas such as hydrogen, use a mass flow controller (1')
After the flow rate is controlled in the stainless steel container (3'), the organic metal is contained in the organic metal (4') sealed in the stainless steel container (3').
有機金属（４′）は恒温槽（５′）中で冷媒（６′）に
より低温に保たれている。有機金属を含むガスは、配管
径を小さくしたコンダクタンスライン（８′）およびニ
ードルバルブ（９′）によって構成される流体抵抗物を
通って、図示されていないリアクタに導入される。有機
金属（４′）内における圧力は圧力計（２′）により測
定され、一定値（本実施例では７６０Ｔｏｒｒ）となる
ようにニードルバルブ（９′）の開度が自動調節される
。圧力計（２′）および（７′）の測定値の差から、コ
ンダクタンスライン（８′）における圧力損失を知るこ
とができる。この場合、ステンレス容器（３′）内にお
ける圧力損失はコンダクタンスライン（８′）内に比較
して無視できる程度になっている。一方、キャリアガス
のみのコンダクタンスライン（８′）における圧力損失
は、キャリアガスをバイパスライン（１０’）に通し、
圧力計（２′）および（７′）の測定値の差から知るこ
とができる。この二つの圧力損失から、キャリアガスに
含まれる有機金属ガスの含有重重１％）を知ることがで
きる。The organic metal (4') is kept at a low temperature by a refrigerant (6') in a constant temperature bath (5'). The organic metal-containing gas is introduced into a reactor (not shown) through a fluid resistor constituted by a conductance line (8') with a reduced piping diameter and a needle valve (9'). The pressure inside the organic metal (4') is measured by a pressure gauge (2'), and the opening degree of the needle valve (9') is automatically adjusted so as to maintain a constant value (760 Torr in this example). The pressure loss in the conductance line (8') can be determined from the difference between the measured values of the pressure gauges (2') and (7'). In this case, the pressure loss within the stainless steel container (3') is negligible compared to that within the conductance line (8'). On the other hand, the pressure loss in the conductance line (8') of only the carrier gas can be reduced by passing the carrier gas through the bypass line (10').
This can be determined from the difference between the measured values of pressure gauges (2') and (7'). From these two pressure losses, it is possible to know the weight (1%) of the organometallic gas contained in the carrier gas.
なお、流体抵抗物はコンダクタンスラインのほか、オリ
フィス、ベントなどの多様な抵抗物でもよく、ニードル
バルブは流れに対する抵抗物が可変であるオリフィスで
もよい。The fluid resistance object may be not only a conductance line but also various resistance objects such as an orifice and a vent, and the needle valve may be an orifice whose resistance to flow is variable.
以上説明したように本発明によれば、原料ガスの波路に
流体抵抗物を設置し、該流体抵抗物による前記ガスの圧
力損失をモニタしながら原料ガスを供給するため、有機
金属の供給量をモニタしながら、成長膜厚および結晶組
成の制御ができるという優れた効果がある。As explained above, according to the present invention, a fluid resistor is installed in the wave path of the raw material gas, and the raw material gas is supplied while monitoring the pressure loss of the gas due to the fluid resistor, so that the supply amount of the organic metal can be controlled. This has the excellent effect of being able to control the grown film thickness and crystal composition while monitoring.
第１図は本発明にかかる気相結晶成長の原料供給方法の
一実施例の説明図、第２図は従来例の説明図である。
１．１′・・・マスフローコントローラ、 ２．２’
７′・・・圧力計、 ３．３′・・・ステンレス容器、
４．４′・・・有機金属、 ５．５′・・・恒温槽、
６゜６′・・・冷媒、 ８′・・・コンダクタンスラ
イン、９、９′・・・ニードルバルブ、 １０′・・
・バイパスライン。FIG. 1 is an explanatory diagram of an embodiment of the raw material supply method for vapor phase crystal growth according to the present invention, and FIG. 2 is an explanatory diagram of a conventional example. 1.1'...mass flow controller, 2.2'
7'...Pressure gauge, 3.3'...Stainless steel container,
4.4'...Organic metal, 5.5'...Thermostatic chamber,
6゜6'... Refrigerant, 8'... Conductance line, 9, 9'... Needle valve, 10'...
・Bypass line.
Claims (1)
相結晶成長の原料供給方法において、前記原料ガスの流
路に流体抵抗物を設置し、該流体抵抗物による前記ガス
の圧力損失をモニタしながら原料ガスを供給することを
特徴とする気相結晶成長の原料供給方法。In a raw material supply method for vapor phase crystal growth in which gas phase crystal growth is performed using a raw material gas containing an organic metal, a fluid resistance object is installed in the flow path of the raw material gas, and the pressure loss of the gas due to the fluid resistance object is reduced. A raw material supply method for vapor phase crystal growth characterized by supplying raw material gas while monitoring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24672788A JPH0292894A (en) | 1988-09-30 | 1988-09-30 | Method for feeding raw material in vapor-phase crystal growth process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24672788A JPH0292894A (en) | 1988-09-30 | 1988-09-30 | Method for feeding raw material in vapor-phase crystal growth process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0292894A true JPH0292894A (en) | 1990-04-03 |
Family
ID=17152748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24672788A Pending JPH0292894A (en) | 1988-09-30 | 1988-09-30 | Method for feeding raw material in vapor-phase crystal growth process |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0292894A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023047087A (en) * | 2021-09-24 | 2023-04-05 | 株式会社Kokusai Electric | Gas supply system, wafer processing device, manufacturing method of semiconductor device and program |
-
1988
- 1988-09-30 JP JP24672788A patent/JPH0292894A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023047087A (en) * | 2021-09-24 | 2023-04-05 | 株式会社Kokusai Electric | Gas supply system, wafer processing device, manufacturing method of semiconductor device and program |
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