JPH0222199A - Epitaxial growth method in vapor phase - Google Patents
Epitaxial growth method in vapor phaseInfo
- Publication number
- JPH0222199A JPH0222199A JP17324288A JP17324288A JPH0222199A JP H0222199 A JPH0222199 A JP H0222199A JP 17324288 A JP17324288 A JP 17324288A JP 17324288 A JP17324288 A JP 17324288A JP H0222199 A JPH0222199 A JP H0222199A
- Authority
- JP
- Japan
- Prior art keywords
- growth
- vapor phase
- furnace
- base plate
- epitaxial growth
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000012808 vapor phase Substances 0.000 title claims abstract description 14
- 239000007789 gas Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000012535 impurity Substances 0.000 abstract description 20
- 238000005530 etching Methods 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008034 disappearance Effects 0.000 abstract description 2
- 230000000630 rising effect Effects 0.000 abstract 3
- 230000000977 initiatory effect Effects 0.000 abstract 2
- 229910052814 silicon oxide Inorganic materials 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 15
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000000927 vapour-phase epitaxy Methods 0.000 description 2
- 238000001947 vapour-phase growth Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910002059 quaternary alloy 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、化合物半導体の気相エピタキシャル成長方法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for vapor phase epitaxial growth of compound semiconductors.
従来、化合物半導体の気相エピタキシャル成長方法とし
て、クロライドＶ Ｐ Ｅ （Ｖａｐｏｒ Ｐｈａｓ
ｅＥｐｉｔａｘｙ ） 、ハイドライドＶＰＥ、 ＭＯ
（ＭｅｔａｌＯｒｇａｎｉｃ ） ＶＰＥなどがある。Conventionally, as a vapor phase epitaxial growth method for compound semiconductors, chloride V P E (Vapor Phas
eEpitaxy), Hydride VPE, MO
(Metal Organic) VPE, etc.
第３図は従来例を説明するためのｎ−ＩｎＰ結晶中の不
純物濃度と結晶の深さの関係を示す相関図である。上述
した方法により半導体基板上にホモあるいはへテロのエ
ピタキシャル層を堆積する場合、第３図に示すように、
石英反応管やガスソース、メタルソースからのシリコン
不純物が基板−エピタキシャルの界面に集まり、不純物
濃度のピークを示する傾向がある。FIG. 3 is a correlation diagram showing the relationship between the impurity concentration in an n-InP crystal and the crystal depth for explaining a conventional example. When a homo- or hetero-epitaxial layer is deposited on a semiconductor substrate by the method described above, as shown in FIG.
Silicon impurities from the quartz reaction tube, gas source, and metal source tend to collect at the substrate-epitaxial interface and exhibit a peak in impurity concentration.
上述した従来の気相エピタキシャル成長方法では、上述
した界面への不純物の堆積を、高温での気相エツチング
により除去し、その後、エピタキシャル成長へ進むのが
一般的である。しかし、エツチングプロセスは、高温に
しなければ基板表面の鏡面性を保持できないばかりでな
く、基板に含まれている不純物がエピタキシャル層に取
り込まれてしまう欠点がある。In the conventional vapor phase epitaxial growth method described above, it is common to remove the impurity deposited on the interface by vapor phase etching at high temperature, and then proceed to epitaxial growth. However, the etching process has the disadvantage that not only the specularity of the substrate surface cannot be maintained unless the etching process is carried out at high temperatures, but also impurities contained in the substrate are incorporated into the epitaxial layer.
本発明の目的は、シリコン不純物の基板＝エピタキシャ
ル界面の不純物のピークを消滅させ、高温での気相エツ
チングが不要な気相エピタキシャル成長方法を提供する
ことにある。An object of the present invention is to provide a vapor phase epitaxial growth method that eliminates the impurity peak at the substrate=epitaxial interface of silicon impurities and eliminates the need for vapor phase etching at high temperatures.
本発明の気相エピタキシャル成長方法は、化合物半導体
の気相エピタキシャル成長法において、反応管内の昇温
工程中エピタキシャル成長を開始する直前まセ雰囲気ガ
ス中に酸素を添加することにより構成される。The vapor phase epitaxial growth method of the present invention is configured by adding oxygen to the atmospheric gas immediately before starting epitaxial growth during the temperature raising step in the reaction tube in the vapor phase epitaxial growth method of compound semiconductors.
次に、本発明の実施例について図面を参照して説明する
。本実施例では、ｎ−ＩｎＰ層の成長について説明する
。Next, embodiments of the present invention will be described with reference to the drawings. In this example, growth of an n-InP layer will be explained.
第１図（ａ）〜（ｄ）は本発明の方法の実施例を説明す
るためのｎ−ＩｎＰ結晶中の不純物濃度と結晶の深さの
関係を示す相関図、第２図は本発明の方法を実現するた
めのハイ下ライト気相成長装置の断面図である。二成長
室反応管１には、ホスフィン、ドーパントを供給するＶ
族管７と水素、塩化水素を供給するキャリヤー導入管８
が接続され、二成長室反応管１内にＩｎソース４とＧａ
ソース５がそれぞれ設置されている。Ｆｅドープの半絶
縁性ＩｎＰ基板２は、昇温工程ではＢ炉に位置し、Ｉｎ
Ｐの成長を開始°する時点でＡ炉の位置まで回転により
移動する。Ｂ炉の雰囲気ガスは、昇温前は水素のみ、昇
温中は水素とＩｎＰ基板２の熱劣化防止用のホスフィン
、成長中は水素のみ、降温時はエピタキシャル成長済Ｉ
ｎＰ基板２の熱劣化防止用ホスフィンと水素、熱劣化の
心配がない温度まで下がればホスフィンは止められる。FIGS. 1(a) to (d) are correlation diagrams showing the relationship between the impurity concentration in an n-InP crystal and the depth of the crystal for explaining an example of the method of the present invention, and FIG. FIG. 2 is a cross-sectional view of a highlight vapor phase growth apparatus for implementing the method. Two growth chamber reaction tubes 1 are supplied with V for supplying phosphine and dopants.
Group pipe 7 and carrier introduction pipe 8 for supplying hydrogen and hydrogen chloride
are connected, and an In source 4 and a Ga
Sources 5 are installed respectively. The Fe-doped semi-insulating InP substrate 2 is located in the B furnace during the temperature raising process, and the InP substrate 2 is
At the point in time when P growth is to begin, it is rotated to the position of furnace A. The atmospheric gas in the B furnace is only hydrogen before heating up, hydrogen and phosphine for preventing thermal deterioration of the InP substrate 2 during heating, only hydrogen during growth, and only hydrogen after epitaxial growth when cooling down.
Phosphine and hydrogen are used to prevent thermal deterioration of the nP substrate 2. Phosphine is stopped when the temperature drops to a point where there is no risk of thermal deterioration.
Ａ炉の雰囲気ガスは、成長開始数分前から水素、ホスフ
ィン及び塩化水素を導入して定常的な雰囲気を作り、Ｂ
炉からの基板２の回転移動、すなわち成長開始にそなえ
る。ＩｎＧａＡｓやＩｎＧａＡｓＰ等の三元系、や四元
系の場合は、上述した説明とは逆に、昇温中の基板待機
にはＡ炉を用い、成長にＢ炉を用いることになる。For the atmospheric gas in furnace A, hydrogen, phosphine, and hydrogen chloride are introduced several minutes before the start of growth to create a steady atmosphere.
Rotational movement of the substrate 2 from the furnace, ie, preparation for the start of growth. In the case of a ternary system or a quaternary system such as InGaAs or InGaAsP, contrary to the above explanation, the A furnace is used for waiting the substrate during temperature rise, and the B furnace is used for growth.
以上説明した装置により、まず、Ｂ炉の雰囲気ガスに昇
温中は水素とＩｎＰ基板２の熱劣化防止用のホスフィン
のみという従来通りのガスを用いて、Ｆｅドープ半絶縁
性ＩｎＰ基板２上に成長したエピタキシャル層の深さ方
向不純物濃度分布を測定した結果が第１図（ｃ）に示し
である。同図により明らかなように、表面からの深さが
基板−エピタキシャル界面と思われる位置に不純物濃度
のピークが発生している。このピークの高さや幅は成長
毎に変動する。ピークを形成する元素はシリコンである
ことは、ＳＩＭＳ分析により同定されている。次に、昇
温中のＢ炉の雰囲気ガスに酸素を３ｐｐｍ添加した時の
基板２上に成長したエピタキシャル層の深さ方向不純物
濃度分布を測定した結果を第１図（ａ）に示す、同図か
ら明らかなように、第１図（ｃ）のようなピークは完全
に消滅している。更に、酸素をｉｐｐｍ添加した時の結
果を第１図（ｂ）に示す、この場合、３ｐｐｍ添加した
時に比べ完全にはピークが消滅していないが、酸素無添
加の場合よりも、明らかにピークの減少が見られる０以
上の結果より、昇温中のＢ炉の雰囲気ガスに酸素を添加
することにより、基板−エピタキシャル界面位置に表れ
る不純物濃度のピークを制御できることがわかる０次に
、エピタキシャル成長中の雰囲気ガス、すなわち、Ａ炉
の雰囲気ガス中に酸素を３ｐｐｍ添加した結果を第１図
（ｄ）に示す、これから明らかなように、エピタキシャ
ル層全体の不純物濃度は下がっているが、基板−エピタ
キシャル界面のピークには影響しない、この結果より、
ピークの消滅は、基板２の表面に吸着しているシリコン
が、酸素により、Ｓ １−Ｏｘという不活性な形態なる
ためと考えることができる。Using the apparatus described above, first, a conventional gas consisting of only hydrogen and phosphine for preventing thermal deterioration of the InP substrate 2 is used as the atmospheric gas in the B furnace during heating, and a Fe-doped semi-insulating InP substrate 2 is coated. The results of measuring the impurity concentration distribution in the depth direction of the grown epitaxial layer are shown in FIG. 1(c). As is clear from the figure, a peak of impurity concentration occurs at a position deep from the surface that is considered to be the substrate-epitaxial interface. The height and width of this peak vary with growth. It has been identified by SIMS analysis that the element forming the peak is silicon. Next, the results of measuring the impurity concentration distribution in the depth direction of the epitaxial layer grown on the substrate 2 when 3 ppm of oxygen was added to the atmospheric gas of the B furnace during heating are shown in Figure 1(a). As is clear from the figure, the peak shown in FIG. 1(c) has completely disappeared. Furthermore, the results when ippm of oxygen was added are shown in Figure 1 (b). In this case, the peak did not disappear completely compared to when 3 ppm was added, but the peak was clearly stronger than when no oxygen was added. From the results of 0 or more where a decrease in 0 is observed, it is clear that by adding oxygen to the atmospheric gas of the B furnace during heating, the peak of impurity concentration appearing at the substrate-epitaxial interface position can be controlled. Figure 1(d) shows the result of adding 3 ppm of oxygen to the atmospheric gas of the A furnace, that is, the atmospheric gas of the A furnace.As is clear from this, the impurity concentration of the entire epitaxial layer has decreased, but the From this result, it does not affect the interface peak.
The disappearance of the peak can be considered to be because the silicon adsorbed on the surface of the substrate 2 is converted into an inert form called S1-Ox by oxygen.
以上、ｎ−ＩｎＰ層の成長について説明したが、本発明
は、Ｉ ｎＧａＡｓやＩｎＧａＡｓＰ等を成長する場合
でも同様な効果を有するばかりでなく、クロライドＶＰ
ＥやＭＯＶＰＥについても同様な効果を得られる。Although the growth of an n-InP layer has been described above, the present invention not only has similar effects when growing InGaAs, InGaAsP, etc.
Similar effects can be obtained with E and MOVPE.
以上説明したように、本発明は、エピタキシャル成長反
応管内の昇温工程中に、成長を開始する直前まで雰囲気
ガス中に微量の酸素を添加することにより、シリコン不
純物の基板−エピタキシャル界面の不純物のピークを消
滅させ、高温での気相エツチングを不要にすることがで
きるという効果がある。As explained above, the present invention is capable of peaking impurity levels at the substrate-epitaxial interface of silicon impurities by adding a small amount of oxygen to the atmospheric gas during the temperature raising process in the epitaxial growth reaction tube until just before the growth starts. This has the effect of eliminating the need for vapor phase etching at high temperatures.
第１図（ａ）〜（ｄ）は本発明の方法の実施例を説明す
るためのｎ−ＩｎＰ結晶中の不純物濃度と結晶の深さの
関係を示す相関図、第２図は本発明を実現するためのハ
イドライド気相成長装置の断面図、第３図は従来例を説
明するためのｎ−ＩｎＰ結晶中の不純物濃度と結晶の深
さの関係を示す相関図である。
１・・・二成長室成長管、２・・・Ｉｎ基板、３・・・
ホルダー、４・・・Ｉｎソース、５・・・Ｇａソース、
６・・・Ｉｎソース、７・・・Ｖ族管、８・・・キャリ
ヤー導入管。
表面かＳの濯之（Ａ丸）
（Ｑ）
基面〆・らの５７さびり
第
図
表面力・Ｓの濯ぎ（Ａｆｆ＝） 表面からの源屓ス
ｍ）（凡）（ｂ）
銅１
〜ヤリャ４ Ｘｖ
第２図FIGS. 1(a) to (d) are correlation diagrams showing the relationship between the impurity concentration in an n-InP crystal and the crystal depth for explaining an example of the method of the present invention, and FIG. FIG. 3 is a cross-sectional view of a hydride vapor phase growth apparatus for realizing the present invention, and is a correlation diagram showing the relationship between the impurity concentration in an n-InP crystal and the crystal depth to explain a conventional example. 1...Two growth chamber growth tubes, 2...In substrate, 3...
holder, 4...In source, 5...Ga source,
6...In source, 7...V group tube, 8...Carrier introduction tube. Rinsing of surface or S (circle A) (Q) 57 Rust diagram of base surface/ra Surface force/rinsing of S (Aff=) Source from surface m) (general) (b) Copper 1 ~ Yalya 4 Xv Figure 2
Claims (1)
応管内の昇温工程中エピタキシャル成長を開始する直前
まで雰囲気ガス中に酸素を添加することを特徴とする気
相エピタキシャル成長方法。A vapor phase epitaxial growth method for compound semiconductors, characterized in that oxygen is added to an atmospheric gas during a temperature raising step in a reaction tube until just before epitaxial growth is started.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17324288A JP2661155B2 (en) | 1988-07-11 | 1988-07-11 | Vapor phase epitaxial growth method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17324288A JP2661155B2 (en) | 1988-07-11 | 1988-07-11 | Vapor phase epitaxial growth method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0222199A true JPH0222199A (en) | 1990-01-25 |
| JP2661155B2 JP2661155B2 (en) | 1997-10-08 |
Family
ID=15956794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17324288A Expired - Lifetime JP2661155B2 (en) | 1988-07-11 | 1988-07-11 | Vapor phase epitaxial growth method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2661155B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110777432A (en) * | 2018-07-30 | 2020-02-11 | 赛奥科思有限公司 | Nitride crystal |
| CN110777433A (en) * | 2018-07-30 | 2020-02-11 | 赛奥科思有限公司 | Nitride crystal |
-
1988
- 1988-07-11 JP JP17324288A patent/JP2661155B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110777432A (en) * | 2018-07-30 | 2020-02-11 | 赛奥科思有限公司 | Nitride crystal |
| CN110777433A (en) * | 2018-07-30 | 2020-02-11 | 赛奥科思有限公司 | Nitride crystal |
| CN110777433B (en) * | 2018-07-30 | 2023-09-29 | 住友化学株式会社 | nitride crystal |
| CN110777432B (en) * | 2018-07-30 | 2023-09-29 | 住友化学株式会社 | nitride crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2661155B2 (en) | 1997-10-08 |
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