JPH0551559B2 - - Google Patents
Info
- Publication number
- JPH0551559B2 JPH0551559B2 JP59118430A JP11843084A JPH0551559B2 JP H0551559 B2 JPH0551559 B2 JP H0551559B2 JP 59118430 A JP59118430 A JP 59118430A JP 11843084 A JP11843084 A JP 11843084A JP H0551559 B2 JPH0551559 B2 JP H0551559B2
- Authority
- JP
- Japan
- Prior art keywords
- flow rate
- growth
- organometallic
- ratio
- reaction tube
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/14—Feed and outlet means for the gases; Modifying the flow of the reactive gases
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、半導体素子を作製するときに使われ
る有機金属気相エピタキシヤル成長方法（以下
MOCVD方法とする。）に関するものである。[Detailed Description of the Invention] Industrial Application Field The present invention relates to an organometallic vapor phase epitaxial growth method (hereinafter referred to as
Use MOCVD method. ).
従来例の構成とその問題点
有機金属気相エピタキシヤル成長装置は、多く
の半導体素子の電気的・光学的性質を決定づける
薄膜の作製に用いられる。この薄膜の電気的・光
学的性質およびそのウエハ面内での均一性、ウエ
ハ間での再現性を決定づける一要因に、有機金属
気相エピタキシヤル成長装置の成長用材料ガス供
給配管系の構成があげられる。従来の配管系の構
成は、成長反応管に近い側から説明すると、２系
列の配管からなる。１つは、有機金属材料を供給
するものであり、他は、水素化物材料、ハロゲン
化物材料を供給するものである。そのそれぞれ
が、さらに各材料個別の配管に分けられ、構成さ
れている。この構成で有機金属材料を供給するに
は、キヤリアガス、例えばH2などを有機金属材
料中でバブルしたり、吹きつけたりする。通常、
恒温槽に入れられた有機金属材料の温度で、この
材料の蒸気圧を制御し、キヤリアガスの量とで、
有機金属材料供給量を制御し、作製する薄膜の電
気的・光学的性質を制御する。しかしながら、こ
の方法では、有機金属材料が混合し、成長反応管
へ行くまでの径路が長いと、一部の有機金属材料
同志で化学反応が起きたり、温度の異なる有機金
属材料が混合するため、配管内壁に析出したりす
るという問題がある。また、有機金属材料をそれ
ぞれ個別の配管で成長反応管に導入すると上記問
題点は緩和されるが、それぞれの配管内の流量が
異なると、流量の少ない材料ガスが流量の多いガ
スに圧迫され、ハンチング等を起こし、混晶の組
成やキヤリア濃度などが変化する。デバイス作製
の時には、この問題も大きく、デバイスの電気
的・光学的特性を左右する。Conventional Structures and Problems Metalorganic vapor phase epitaxial growth apparatuses are used to fabricate thin films that determine the electrical and optical properties of many semiconductor devices. One of the factors that determines the electrical and optical properties of this thin film, its uniformity within the wafer plane, and its reproducibility between wafers is the configuration of the growth material gas supply piping system of the organometallic vapor phase epitaxial growth apparatus. can give. The configuration of a conventional piping system, starting from the side closest to the growth reaction tube, consists of two lines of piping. One supplies organometallic materials, and the other supplies hydride and halide materials. Each of these is further divided into individual piping for each material. To supply the organometallic material in this configuration, a carrier gas, such as H2 , is bubbled or blown into the organometallic material. usually,
The temperature of the organometallic material placed in a constant temperature bath controls the vapor pressure of this material, and the amount of carrier gas
The amount of organic metal material supplied is controlled to control the electrical and optical properties of the thin film produced. However, in this method, if the organometallic materials are mixed and the path to the growth reaction tube is long, chemical reactions may occur between some of the organometallic materials, or organometallic materials at different temperatures may be mixed. There is a problem that it may deposit on the inner wall of the piping. In addition, if the organometallic materials are introduced into the growth reaction tube through separate pipes, the above problems can be alleviated, but if the flow rates in each pipe are different, the material gas with a low flow rate will be compressed by the gas with a high flow rate. Hunting occurs, and the composition of the mixed crystal and carrier concentration change. This problem is also a major problem when manufacturing devices, and affects the electrical and optical characteristics of the device.
発明の目的
本発明は上記欠点に鑑み、所望の薄膜の電気
的・光学的性質を制御性良く、ウエハ面内での均
一性良く、しかもウエハ間での再現性も良く作製
することを可能とする有機金属気相エピタキシヤ
ル成長方法を提供するものである。Purpose of the Invention In view of the above drawbacks, the present invention makes it possible to manufacture desired thin films with good controllability of electrical and optical properties, good uniformity within the wafer surface, and good reproducibility between wafers. The present invention provides a metal organic vapor phase epitaxial growth method.
発明の構成
この目的を達成するために、本発明の
MOCVD方法は、成長反応管に、個別の配管に
より有機金属材料を導入し、それぞれの配管内を
同時に流れるガスの流量の最大値に対する最小値
の比が１／10以上である様に流量を設定すること
により構成される。この構成により、電気的・光
学的性質の制御性、ウエハ面内での均一性、ウエ
ハ間での再現性の良い薄膜を作製することができ
る。Structure of the Invention To achieve this objective, the present invention
In the MOCVD method, the organic metal material is introduced into the growth reaction tube through individual piping, and the flow rate is set so that the ratio of the minimum to maximum flow rate of gas flowing simultaneously in each piping is 1/10 or more. It consists of: With this configuration, it is possible to produce a thin film with good controllability of electrical and optical properties, uniformity within the wafer surface, and good reproducibility between wafers.
実施例の説明
本発明のMOCVD方法について、その一実施
例を第１図を用いて具体的に説明する。DESCRIPTION OF EMBODIMENTS One embodiment of the MOCVD method of the present invention will be specifically described with reference to FIG.
第１図の構成は、GaAs系、GaAlAs系材料を
用いて結晶成長を行なうものとなつている。この
構成では、Ｐ型ドーパントとして、Znをジメチ
ル亜鉛（以下DMZ）の形で、ｎ型ドーパントと
して、Seをセレン化水素、H2Seの形で用いる。 The configuration shown in FIG. 1 is for crystal growth using GaAs-based or GaAlAs-based materials. In this configuration, Zn is used as a P-type dopant in the form of dimethylzinc (hereinafter referred to as DMZ), and Se is used as an n-type dopant in the form of hydrogen selenide, H 2 Se.
一例として、アンドープ＝GaAlAsの結晶成長
の場合を考える。従来の方法では、有機金属槽１
中のトリメチルガリウム（以下TMG）をH2をキ
ヤリアガスとして輸送路４を介して、成長反応管
８に導く。同様に有機金属槽２中のトリメチルア
ルミニウム（以下TMA）を輸送路５を介して導
く。他方、輸送路７により、アルシンをH2をキ
ヤリアガスとして成長反応管８に導き、結晶成長
を行なつた。成長温度は750℃、Ｖ族元素の
族元素に対するモル比30、全ガス流量５／分、
成長速度2μm／時で２時間結晶成長を行なつた。
有機金属槽１は−10℃、有機金属槽２は20℃に保
ち、TMGのキヤリアH2ガスは、５c.c.／分、
TMAは、５c.c.／分としたところ、ｎ型のGa1-x
AlxAsが成長した。この時の成長結晶の混晶比ｘ
のバラツキ幅Δxをウエハ面内及びエピ層膜厚方
向に、フオトルミネセンス法、Ｘ線マイクロアナ
リシス法、スパツタリング・オージエ電子分光法
を併用して測定した。 As an example, consider the case of undoped GaAlAs crystal growth. In the conventional method, the organometallic bath 1
Trimethyl gallium (hereinafter referred to as TMG) inside is guided to a growth reaction tube 8 via a transport path 4 using H 2 as a carrier gas. Similarly, trimethylaluminum (hereinafter referred to as TMA) in the organometallic tank 2 is guided through the transport path 5. On the other hand, arsine was introduced into a growth reaction tube 8 through a transport path 7 using H 2 as a carrier gas, and crystal growth was performed. The growth temperature was 750°C, the molar ratio of group V elements to group elements was 30, the total gas flow rate was 5/min,
Crystal growth was carried out for 2 hours at a growth rate of 2 μm/hour.
Organometallic bath 1 was kept at -10℃, organometallic bath 2 at 20℃, and TMG's carrier H2 gas was heated at 5c.c./min.
TMA was set at 5 c.c./min, and n-type Ga 1-x
Al x As grew. Mixed crystal ratio x of the growing crystal at this time
The variation width Δx was measured in the plane of the wafer and in the thickness direction of the epitaxial layer using a combination of photoluminescence method, X-ray microanalysis method, and sputtering Auger electron spectroscopy.
一方、本発明の一実施例として、第１図に示す
様に、TMG専用輸送H2ガスライン９、TMA専
用輸送H2ガスライン１０を設け、上記従来例と
同一の成長条件で、前記輸送路９と輸送路１０の
H2ガス流量Ｆだけ変化させ、結晶成長を行ない、
前記と同様の測定方法で混晶比ｘとそのバラツキ
幅Δxを測定した。 On the other hand, as an embodiment of the present invention, as shown in FIG . Route 9 and Transport Route 10
Crystal growth is performed by changing the H2 gas flow rate F,
The mixed crystal ratio x and its variation width Δx were measured using the same measuring method as described above.
第２図に測定結果を示す。輸送路４の流量を
FG、輸送路５の流量をFAとして、
Fnio＝min（FG，FA）
と定義する。ただし、
FG≦FAの時Fnio＝FG
FG＞FAの時Fnio＝FAである。 Figure 2 shows the measurement results. The flow rate of transportation route 4
Define F nio = min (F G , F A ), where F G and the flow rate of transport route 5 are F A . However, when F G ≦ F A , F nio = F G F G > F A , F nio = F A.
また、輸送路７の流量をFnaxとする。 Further, the flow rate of the transportation route 7 is assumed to be F nax .
また混晶比バラツキ幅Δxは、Δx＝xn−ｘと
する、ただしxn：測定した混晶比
ｘ：理論計算より算出した混晶比
についてはデータ数ｎ（≧20）での平均値
を算出し、混晶比ｘにより規格化し、｜
｜／ｘをパラメータとした。 In addition, the mixed crystal ratio variation width Δx is set as Δx=x n −x, where x n : Measured mixed crystal ratio x : Mix crystal ratio calculated from theoretical calculation. For the average value of the number of data n (≧20) Calculate and normalize by the mixed crystal ratio x, |
|/x was used as a parameter.
Fnio／Fnaxを横軸に、｜｜／ｘを縦軸にと
り、白丸は測定値である。実線に示すグラフは、
２次回帰により求めたものである。 F nio /F nax is plotted on the horizontal axis, ||/x is plotted on the vertical axis, and the white circles are measured values. The graph shown by the solid line is
This was determined by quadratic regression.
第２図より、Fnio／Fnaxが１／10より小さくな
るにつれ、｜｜／ｘが大きくなり、Fnio／Fnax
〜１／1000では、｜Δx｜／ｘ〜0.10となる。原因
は明らかではないが、次の事が考えられる。流量
比が小さくなると、FGやFAが時間軸で見て、反
応管内に一定の流量で流れずハンチングを起こし
やすくなる。エピ層膜厚方向で特に｜｜／ｘ
の値が大きくなる事から以上の理由で解釈できる
と考えられる。 From Figure 2, as F nio /F nax becomes smaller than 1/10, ||/x increases, and F nio /F nax
~1/1000, |Δx|/x~0.10. The cause is not clear, but the following may be considered. When the flow rate ratio becomes small, F G and F A do not flow at a constant flow rate in the reaction tube when viewed on the time axis, and hunting tends to occur. Especially in the epi layer thickness direction ||/x
Since the value of becomes large, it can be interpreted for the above reason.
しかしながら、Fnio／Fnax≧１／10では、｜Δx
｜＝0.01と小さく、混晶比の制御性が良い。 However, when F nio /F nax ≧1/10, |Δx
| = 0.01, which is small, and the controllability of the mixed crystal ratio is good.
さらにZnをドーピングしたＰ−GaAlAsの結晶
成長の場合、有機金属材料としてZnが加わり、
輸送路６の流量をFzとし、
Fnio＝min（FG，FA，FZ）
＝min（min（FG，FA），
min（FA，FZ））
と定義されたFnioを用い、混晶比ｘの制御性に加
えてキヤリア濃度ｐの制御性を調べたところ、
Fnio／Fnaxに対して、同様の結果が得られた。 Furthermore, in the case of crystal growth of P-GaAlAs doped with Zn, Zn is added as an organometallic material,
The flow rate of transport route 6 is Fz, and F nio is defined as F nio = min (F G , F A , F Z ) = min (min (F G , F A ), min (F A , F Z ) ) When we investigated the controllability of the carrier concentration p in addition to the controllability of the mixed crystal ratio x using
Similar results were obtained for F nio /F nax .
本実施例では、混晶比とキヤリア濃度の制御
性、均一性、再現性について述べたが、結晶成長
層の膜厚についても同様に制御性、均一性、再現
性が良い。これは結晶成長層の膜厚が、混晶比の
関数となつているためである。 In this example, the controllability, uniformity, and reproducibility of the mixed crystal ratio and carrier concentration have been described, but the controllability, uniformity, and reproducibility of the film thickness of the crystal growth layer are similarly good. This is because the thickness of the crystal growth layer is a function of the mixed crystal ratio.
なお、本実施例では、GaAs系、GaAlAs系材
料を用いて説明したが、本発明は、全ての有機金
属材料を用いたMOCVD成長装置について適用
可能である。 Although this embodiment has been described using GaAs-based and GaAlAs-based materials, the present invention is applicable to MOCVD growth apparatuses using all organic metal materials.
発明の効果
本発明はMOCVD装置において、成長反応管
に個別の配管により有機金属材料を導入し、その
それぞれの配管内を同時に流れるガスの流量の最
大値に対する最小値の比が１／10以上である様に
流量を設定することにより、制御性、均一性、再
現性の良い結晶成長を行なう事ができ、その実用
的効果は著しい。Effects of the Invention The present invention provides an MOCVD apparatus in which an organic metal material is introduced into a growth reaction tube through individual piping, and the ratio of the minimum to maximum flow rate of gas flowing simultaneously in each piping is 1/10 or more. By setting the flow rate in a certain way, crystal growth can be performed with good controllability, uniformity, and reproducibility, and its practical effects are remarkable.
第１図は本発明実施例のMOCVD装置配管系
の概略図、第２図は、流量比Fnio／Fnaxに対する
成長結晶の混晶比のバラツキ幅｜｜／ｘを示
す図である。
１……TMG用有機金属槽、２……TMA用有
機金属槽、３……DMZ用有機金属槽、４，５，
６……輸送路、７……アルシン、セレン化水素、
反応管内の流量制御用キヤリアH2ガスの輸送路、
８……成長反応管、９……TMG専用輸送ライ
ン、１０……TMA専用輸送ライン、１１……
DMZ専用輸送ライン。
FIG. 1 is a schematic diagram of a MOCVD apparatus piping system according to an embodiment of the present invention, and FIG. 2 is a diagram showing the variation width ||/x in the mixed crystal ratio of the grown crystal with respect to the flow rate ratio F nio /F nax . 1...organic metal tank for TMG, 2...organic metal tank for TMA, 3...organic metal tank for DMZ, 4, 5,
6...Transport route, 7...Arsine, hydrogen selenide,
Carrier H2 gas transport path for flow rate control in the reaction tube,
8...Growth reaction tube, 9...Transport line exclusively for TMG, 10...Transport line exclusively for TMA, 11...
DMZ dedicated transport line.
Claims (1)
個別の配管を通して異なる有機金属材料を導入
し、最大流量の配管の流量と最小流量の配管の流
量との比が１／10以上である様に流量を設定する
ことを特徴とする有機金属気相エピタキシヤル成
長方法。1 In the organometallic vapor phase epitaxial growth reaction tube,
A metal-organic gas phase characterized by introducing different metal-organic materials through individual pipes and setting the flow rates so that the ratio of the flow rate of the pipe with the maximum flow rate to the flow rate of the pipe with the minimum flow rate is 1/10 or more. Epitaxial growth method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59118430A JPS60264395A (en) | 1984-06-08 | 1984-06-08 | Vapor-phase epitaxial process for organometallic compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59118430A JPS60264395A (en) | 1984-06-08 | 1984-06-08 | Vapor-phase epitaxial process for organometallic compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60264395A JPS60264395A (en) | 1985-12-27 |
| JPH0551559B2 true JPH0551559B2 (en) | 1993-08-02 |
Family
ID=14736448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59118430A Granted JPS60264395A (en) | 1984-06-08 | 1984-06-08 | Vapor-phase epitaxial process for organometallic compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60264395A (en) |
-
1984
- 1984-06-08 JP JP59118430A patent/JPS60264395A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60264395A (en) | 1985-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4404265A (en) | Epitaxial composite and method of making | |
| US4147571A (en) | Method for vapor epitaxial deposition of III/V materials utilizing organometallic compounds and a halogen or halide in a hot wall system | |
| JPH0529218A (en) | Organic metal molecular beam epitaxial growth method | |
| JP3223575B2 (en) | Compound semiconductor and manufacturing method thereof | |
| JPH0551559B2 (en) | ||
| KR100262018B1 (en) | Compound Semiconductors and Manufacturing Methods Thereof | |
| KR900006120B1 (en) | Epitaxial deposition method of semiconductor material layer using diethyl beryllium as dopant transport compound | |
| JP2885435B2 (en) | Method for manufacturing compound semiconductor thin film | |
| JP3242571B2 (en) | Vapor growth method | |
| JP2793239B2 (en) | Method for manufacturing compound semiconductor thin film | |
| JPS6167221A (en) | Organometal vapor phase epitaxial growth device | |
| EP0138965B1 (en) | Tetramethyltin dopant source for mocvd grown epitaxial semiconductor layers | |
| JPS60176992A (en) | Device for gaseous phase epitaxial growth of organometallic compound | |
| JPH01100976A (en) | Method for manufacturing semiconductor devices | |
| JPH1168235A (en) | Crystal growth method for AlGaAs compound semiconductor and method for manufacturing semiconductor laser | |
| JP2754549B2 (en) | Ga <bottom 0>. ▲ lower 5 ▼ In ▲ lower 0 ▼. (5) Method of growing P crystal | |
| JP2590728B2 (en) | Selective growth method of compound semiconductor | |
| JP2736417B2 (en) | Semiconductor element manufacturing method | |
| JPH0760800B2 (en) | Vapor growth method for compound semiconductors | |
| JPH11126754A (en) | Metalorganic vapor phase epitaxy | |
| JPS6390121A (en) | Vapor phase crystal growth system | |
| JPH08264459A (en) | Chemical beam deposition method and chemical beam deposition apparatus | |
| JPH08288226A (en) | Metalorganic vapor phase growth equipment | |
| JP2740681B2 (en) | Method for manufacturing compound semiconductor thin film | |
| JPH0620050B2 (en) | Gas dilution device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |