JPH03218007A - Semiconductor crystal growing method - Google Patents
Semiconductor crystal growing methodInfo
- Publication number
- JPH03218007A JPH03218007A JP2013278A JP1327890A JPH03218007A JP H03218007 A JPH03218007 A JP H03218007A JP 2013278 A JP2013278 A JP 2013278A JP 1327890 A JP1327890 A JP 1327890A JP H03218007 A JPH03218007 A JP H03218007A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- cell
- crystal
- molecular beam
- heated
- 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
- 239000013078 crystal Substances 0.000 title claims abstract description 30
- 239000004065 semiconductor Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 238000000171 gas-source molecular beam epitaxy Methods 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 238000002109 crystal growth method Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 abstract description 18
- 238000001704 evaporation Methods 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 11
- 230000008020 evaporation Effects 0.000 abstract description 10
- 238000001451 molecular beam epitaxy Methods 0.000 abstract description 9
- 238000005336 cracking Methods 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000011669 selenium Substances 0.000 abstract description 4
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 abstract description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000058 selane Inorganic materials 0.000 abstract description 2
- 239000002178 crystalline material Substances 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001741 metal-organic molecular beam epitaxy Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 150000003342 selenium Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 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、半導体結晶成長方法に係り、特に青色発光ダ
イオードや短波長レーザーなどの発光素子に用いるＩＩ
−ＶＩ族化合物事導体結晶のエピタキシャル成長方法に
関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for growing semiconductor crystals, and in particular to a method for growing semiconductor crystals, particularly for use in II light emitting devices such as blue light emitting diodes and short wavelength lasers.
-Regarding a method for epitaxial growth of a group VI compound conductor crystal.
（従来の技術）
ＩＩ−Ｖｌ族化合物半導体結晶のエピタキシャル成長方
法としてＭ ３ Ｅ （ Ｍｏｌｅｃｕｌａｒ Ｂｅａ
ｍ Ｅｐｉｔａｘｙ）法がある。(Prior art) M3E (Molecular Bea) is a method for epitaxial growth of II-Vl group compound semiconductor crystals.
mEpitaxy) method.
ＭＢＥ法は、超高真空蒸着法の一種で、分子線を基板に
あてて薄膜結晶を成長させる方法である。The MBE method is a type of ultra-high vacuum evaporation method, and is a method of growing thin film crystals by applying molecular beams to a substrate.
従来のＭＢＥ法によるＩＩ−Ｖｌ族化合物半導体の結晶
成長方法は以下の様なものであった。 第２図は従来の
ＭＢＥ装置１０の概略断面図である。The conventional method for growing crystals of II-Vl group compound semiconductors using the MBE method is as follows. FIG. 2 is a schematic cross-sectional view of a conventional MBE apparatus 10.
同図において、１１はＭＢＥチャンバーであり、１２は
分子Ｉ１蒸発源セル、１３はＭＢＥチャンバー１１を冷
却するための液体窒素シュラウドである。In the figure, 11 is an MBE chamber, 12 is a molecule I1 evaporation source cell, and 13 is a liquid nitrogen shroud for cooling the MBE chamber 11.
また、チャンバー１１の中心部にはモリブデン等からな
る支持台１４が設置され、この上に半導体基板結晶１５
を支持する様になっている。Further, a support base 14 made of molybdenum or the like is installed in the center of the chamber 11, and a semiconductor substrate crystal 15 is placed on this support base 14.
It seems to support the.
また、１６は各分子線蒸発源セル１２の分子線の射出口
１２ａの前部に設置されたセルシャッターである。１７
はメインシャッターであり、前記支持台１４の前部に配
置されている。１８は真空測定装置である。Further, 16 is a cell shutter installed in front of the molecular beam exit port 12a of each molecular beam evaporation source cell 12. 17
is a main shutter, which is arranged in front of the support base 14. 18 is a vacuum measuring device.
従来、ＭＢＥ装Ｉ！１０を使用して次の様にして結晶成
長を行なっていた。Previously, MBE-equipped I! Crystal growth was carried out using No. 10 in the following manner.
まず、装置自体の不純物を除去するために、チャンバー
１１内を加熱することによりベーキングを行なう。次に
、例えば、ｍｂ 族の原料としてＺｎ、■ｂ 族の原
料としてＳｅを用い、それぞれの原料を分子線蒸発源セ
ル１２に充填し、所望の分子線憬になる様に加熱保持し
ておく。First, in order to remove impurities from the device itself, baking is performed by heating the inside of the chamber 11. Next, for example, using Zn as the mb group raw material and Se as the b group raw material, the respective raw materials are filled into the molecular beam evaporation source cell 12 and heated and held to obtain the desired molecular beam concentration. .
そして、分子線蒸発源セル１２より所定の分子を蒸発さ
せ、あらかじめ設定温度にしておいたモリブデン製の基
板支持台１４上に固定されたＧａＡＳ基板結晶１５の上
に、ＺｎＳｅの単結晶を結晶成長させる。Then, predetermined molecules are evaporated from the molecular beam evaporation source cell 12, and a ZnSe single crystal is grown on the GaAS substrate crystal 15 fixed on the molybdenum substrate support 14, which has been set at a preset temperature. let
（発明が解決しようとする課題）
この様な従来の半導体結晶成長方法においては、蒸気圧
の高い材料を用いているので、従来のＭＢＥ装置１０を
用いた場合には、高温ベーキングができないため、真空
度が上らず残留不純物が多いものであった。(Problems to be Solved by the Invention) Since such conventional semiconductor crystal growth methods use materials with high vapor pressure, high-temperature baking cannot be performed using the conventional MBE apparatus 10. The degree of vacuum could not be increased and there were many residual impurities.
また、液相成長方法に比べ、低温成長、非平衡状態の成
長であるが、自己補償効果が起りやすく、格子欠陥の低
減ができないため、良質なＩＩ−Ｖｌ族化合物半導体結
晶が得られなかった。そのため、所望する低抵抗でＰ型
導電性を示す良質な結晶が得られないなどの問題点があ
った。In addition, compared to the liquid phase growth method, the method uses low-temperature growth and non-equilibrium growth, but self-compensation effects tend to occur and lattice defects cannot be reduced, making it impossible to obtain high-quality II-Vl group compound semiconductor crystals. . Therefore, there were problems such as the inability to obtain a high-quality crystal exhibiting the desired low resistance and P-type conductivity.
（課題を解決するための手段）
本発明は上記課題を解決するためになされたものであり
、ＩＩ−ＶＩ族化合物からなる半導体結晶のエピタキシ
ャル成長過程において、Ｇａｓｓ ＳｏｕｒｃｅＭＢＥ
装置を用いて、水素を添加することを特徴とする半導体
結晶成長方法を提供しようとするものである。(Means for Solving the Problems) The present invention has been made to solve the above problems, and in the epitaxial growth process of a semiconductor crystal made of a II-VI group compound, Gas Source MBE
The present invention attempts to provide a semiconductor crystal growth method characterized by adding hydrogen using an apparatus.
（実施例）
本発明はＩｆ−Ｖｌ族化合物半導体結晶の原料に、例え
ば、水素ガス、有灘金属ガスなどの気体を用い、その気
体原料を加熱分解するガスクランキングセルを有するＭ
ＢＥ装置において、エピタキシャル成長中にＩＩｂ族、
■ｂ 族原料分子線と共に水素ガスを基仮に照射する
ことにより、従来技術の問題点である結晶質を向上させ
ようとするものである。(Example) The present invention uses a gas such as hydrogen gas or Nada metal gas as a raw material for an If-Vl group compound semiconductor crystal, and an M having a gas cranking cell for thermally decomposing the gas raw material.
In the BE equipment, during epitaxial growth, group IIb,
(2) By temporarily irradiating hydrogen gas together with the group b source molecular beam, it is attempted to improve the crystallinity, which is a problem with the prior art.
第１図は本発明に使用されるＧａｓ Ｓｏｕｒｃｅ
Ｍ ＢＥ装置（または、ＭＯＭＢＥ装１！）２０である
。Figure 1 shows the gas source used in the present invention.
An MBE device (or MOMBE device 1!) 20.
同図において、２１はチャンバー、２２は固体原料Ｓ一
を加熱蒸発する分子線蒸発源セル、２３は気体原料を加
熱分解するためのがスクラツキングセル、２４は液体窒
素シュラウドである。In the figure, 21 is a chamber, 22 is a molecular beam evaporation source cell for heating and evaporating the solid raw material S1, 23 is a scratching cell for thermally decomposing the gaseous raw material, and 24 is a liquid nitrogen shroud.
このＧａｓ Ｓｏｕｒｃｅ Ｍ Ｂ Ｅ装置２０にお
いても、チｒンバー２１の中心部にモリブデン製の支持
台２５が配置され、この上に半導体基板結晶１５を支持
する様になっている。また、２６は各分子線蒸発源セル
２２及びガスクラツキングセル２３の分子線の出射口２
２ａ及び２３ａの前部に設置されたセルシャッターであ
る。２７はメインシャッターであり、前記支持台２５の
前部に配置されている。In this Gas Source MBE device 20 as well, a support stand 25 made of molybdenum is arranged at the center of the chamber 21, and the semiconductor substrate crystal 15 is supported on this support stand 25. Further, reference numeral 26 denotes a molecular beam exit port 2 of each molecular beam evaporation source cell 22 and gas cracking cell 23.
This is a cell shutter installed in front of 2a and 23a. A main shutter 27 is arranged in front of the support base 25.
同図に示す様なＧａｓ Ｓｏｕｒｃｅ Ｍ Ｂ Ｅ装
置２０において、例えば、分子線蒸発源セル２２に［ｂ
族原料Ｚｎを充填し、ガスクラブキングセル２３に接続
した供給ボンベ２８にはＳｅ，供給ボンベ２９には水素
が封入されている。In the Gas Source MBE device 20 as shown in the same figure, for example, [b
A supply cylinder 28 filled with group raw material Zn and connected to the gas club King cell 23 is filled with Se, and a supply cylinder 29 is filled with hydrogen.
本発明になる半導体結晶成長方法においては、同図に示
したＧａｓ Ｓｏｕｒｃｅ Ｍ Ｂ Ｅ ＠１１ ２
０を用い、まず、２００℃で高温ベーキングを行ない
系内の不純物を低減したのち、Ｚｎ分子線蒸発源セル２
２を所望の分子１ｍ量になる様に加熱保持して、分子線
蒸発源セルよりＺｎ分子を蒸発させる。In the semiconductor crystal growth method according to the present invention, the Gas Source M B E @11 2 shown in the same figure
Using Zn molecular beam evaporation source cell 2, first perform high temperature baking at 200°C to reduce impurities in the system.
Zn molecules are evaporated from the molecular beam evaporation source cell by heating and maintaining Zn to a desired molecular weight of 1 m.
一方、Ｓｅ供給ボンベ２８より、例えば、水素化セレン
ガスをＭ Ｆ Ｃ （ Ｍａｓｓ Ｆｌｏｗ Ｃｏｎｔ
ｒｏｌｌｅｒ）３０により流量制御し、ガスクラッキン
グセル２３により加熱分解したものと、更に、Ｈ２供給
ボンベ２９よりＨ２をＭＦＣ３１により流量制御し、ガ
スクラッキング３２にて加熱分解したものとを同時供給
し、所定の温度に加熱保持された基板支持台２５に固定
されたＧａＡｓ基板結晶１５上に堆積させ、ＺｎＳｅの
単結晶を作製するものである。On the other hand, from the Se supply cylinder 28, for example, hydrogenated selenium gas is supplied to MFC (Mass Flow Cont
At the same time, H2 is supplied from an H2 supply cylinder 29 with a flow rate controlled by an MFC 31 and thermally decomposed by a gas cracking cell 23, and H2 is heated to a predetermined level. A single crystal of ZnSe is produced by depositing it on a GaAs substrate crystal 15 fixed to a substrate support 25 heated and maintained at a temperature of .
以下に具体例を示す。A specific example is shown below.
前記Ｇａｓ Ｓｏｕｒｃｅ Ｍ Ｂ Ｅ装置において
、ＧａＡＳ絶縁基板の（１００）結晶面上に、Ｉｂ族原
料としてＺｎ、ｖｔｂ族原料として水素化セレンガスを
用い、更に水素ガスをエピタキシャル成長に加えること
により、Ｚ’ｎ３ｅ単結晶を作製する。In the Gas Source MBE device, Z'n3e is grown on the (100) crystal plane of the GaAS insulating substrate by using Zn as the Ib group raw material and selenium hydride gas as the Vtb group raw material, and further adding hydrogen gas to the epitaxial growth. Create a single crystal.
なお、この結晶成長に用いた原料ガスの分子線最及び流
−はそれぞれＺｎ ５．４ｘ １０ ＴｏｒｒＨ ２
３ ｅ ０．４ 〜１．６ ＳＣＣＨ ， Ｈ
２は １．Ｏ ＳＣＣＨで成長基板温度は２００℃で
、成長前のｂａｃｋ ｇｒｏｕｎｄｐｒｅｓｓｕｒｅは
、約５ｘｌＯ Ｔｏｒｒあった。Note that the molecular beam length and flow of the raw material gas used for this crystal growth are Zn 5.4x 10 TorrH 2 respectively.
3 e 0.4 ~ 1.6 SCCH, H
2 is 1. The growth substrate temperature in the OSCCH was 200° C., and the back ground pressure before growth was about 5×1O Torr.
上記の様な条件の下で作製した結晶をｖａｎｄｅｒ ｐ
ａＷ法及び７７Ｋの７ォトルミネッセンス法（ＨｅＣｄ
レーザ３２５ｎｌ． ５＋＋Ｗ励起）により測定した４
４５ｒｖ近｛労の強度ＩＳ、ホール移動度μ及び、キャ
リア濃度ＮＯは、次表の様になった。The crystals produced under the above conditions were subjected to vander p
aW method and 77K 7 photoluminescence method (HeCd
Laser 325nl. 4 measured by 5++W excitation)
45rv near {labor intensity IS, hole mobility μ, and carrier concentration NO were as shown in the following table.
表
表からわかる様に、水素を添加することにより、ホール
移動度μが向上し、キャリア濃度ＮＯの増加が見られ、
それに伴い、ＺｎＳｅの発光波長である４４５ｎ一近傍
、即ち、青色発光領域において著しく発光強度ＩＳが向
上した。As can be seen from the table, by adding hydrogen, the hole mobility μ improves and the carrier concentration NO increases.
Accordingly, the emission intensity IS was significantly improved in the vicinity of 445n, which is the emission wavelength of ZnSe, that is, in the blue emission region.
（発明の効果）
上述の様に、本発明になる半導体結晶成長方法によれば
、■−■族化合物からなる半導体結晶のエピタキシャル
成長過程において、水素を添加することを特徴としたの
で、結晶中の格子欠陥をなくす効果があり、結晶質を向
上させるものである。(Effects of the Invention) As described above, according to the semiconductor crystal growth method of the present invention, hydrogen is added in the epitaxial growth process of the semiconductor crystal made of the ■-■ group compound. It has the effect of eliminating lattice defects and improves crystal quality.
また、非発光性再結合を減らし、発光性再結合を増加さ
せ発光特性を向■きせるので、発光特性が向上し、 ひ
いては、従来、困難であった低抵抗のＰ型半導体の成長
も可能となる等、導電性の制御が可能な半導体結晶成長
方法の提供を可能とするものである。In addition, it reduces non-radiative recombination and increases radiative recombination, which improves the light-emitting properties, making it possible to grow low-resistance P-type semiconductors, which was previously difficult. This makes it possible to provide a semiconductor crystal growth method that allows control of conductivity.
第１図は本発明に使用されるＧａｓ Ｓａｕｃｅ Ｍ
Ｂ Ｅ装置（または、ＭＯＭＢＥ装置）、第２図は従来
のＭＢＥ装置１０の概略断面図である。
１５・・・半導体基板結晶、
２ ０ ・ＧａＳＳｏｕｒｃｅ ｌｙｌ Ｂ Ｅ装置
、２１・・・チャンバー、２２−・・分子線蒸発源セル
、２３、３２・・・ガスクラッキングセル、２４・・・
液体窒素シュラウド、２５・・・支持台、２６・・・セ
ルシャッタタ−
２７・・・メインシャッター
２８、２９、・・・供給ボンベ、
３０、３１・・・ＭＦＣ．
特 許 出願人
日本ビクター株式会社
代表者 垣木 邦夫
第
１
図Figure 1 shows Gas Sauce M used in the present invention.
BE Apparatus (or MOMBE Apparatus) FIG. 2 is a schematic cross-sectional view of a conventional MBE apparatus 10. DESCRIPTION OF SYMBOLS 15... Semiconductor substrate crystal, 20 - GaSSource lyl BE apparatus, 21... Chamber, 22-... Molecular beam evaporation source cell, 23, 32... Gas cracking cell, 24...
Liquid nitrogen shroud, 25... Support stand, 26... Cell shutter 27... Main shutters 28, 29,... Supply cylinder, 30, 31... MFC. Patent Applicant: Japan Victor Co., Ltd. Representative: Kunio Kakiki Figure 1
Claims (1)
長過程において、ＧａｓｓＳｏｕｒｃｅＭＢＥ装置を用
いて、水素を添加することを特徴とする半導体結晶成長
方法A semiconductor crystal growth method characterized by adding hydrogen using a GasSource MBE device during the epitaxial growth process of a semiconductor crystal made of a II-VI group compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013278A JPH03218007A (en) | 1990-01-23 | 1990-01-23 | Semiconductor crystal growing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013278A JPH03218007A (en) | 1990-01-23 | 1990-01-23 | Semiconductor crystal growing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03218007A true JPH03218007A (en) | 1991-09-25 |
Family
ID=11828736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013278A Pending JPH03218007A (en) | 1990-01-23 | 1990-01-23 | Semiconductor crystal growing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03218007A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0418738A (en) * | 1990-05-11 | 1992-01-22 | Mitsubishi Electric Corp | Growth of semiconductor crystal |
-
1990
- 1990-01-23 JP JP2013278A patent/JPH03218007A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0418738A (en) * | 1990-05-11 | 1992-01-22 | Mitsubishi Electric Corp | Growth of semiconductor crystal |
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