JPH0371400B2 - - Google Patents
Info
- Publication number
- JPH0371400B2 JPH0371400B2 JP61126723A JP12672386A JPH0371400B2 JP H0371400 B2 JPH0371400 B2 JP H0371400B2 JP 61126723 A JP61126723 A JP 61126723A JP 12672386 A JP12672386 A JP 12672386A JP H0371400 B2 JPH0371400 B2 JP H0371400B2
- Authority
- JP
- Japan
- Prior art keywords
- crystal
- chamber
- growth
- seed crystal
- single crystal
- 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
- 239000013078 crystal Substances 0.000 claims description 100
- 238000000034 method Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000005092 sublimation method Methods 0.000 claims description 4
- 238000001947 vapour-phase growth Methods 0.000 claims 2
- 239000002994 raw material Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003708 ampul Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 238000002109 crystal growth method Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 2
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
Description
【発明の詳細な説明】
＜産業上の利用分野＞
本発明は、昇華法またはハロゲン輸送法を用い
た−族化合物（ZnS、ZnSe、ZnTe、…）の
バルク単結晶成長方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for growing bulk single crystals of - group compounds (ZnS, ZnSe, ZnTe,...) using a sublimation method or a halogen transport method.
＜従来技術とその問題点＞
ZnS、ZnSe等の−族化合物半導体単結晶
の成長に際しては、従来より一般に昇華法あるい
はハロゲン輸送法を用いられているが、しかしな
がら従来の成長法では、単結晶成長初期に存在す
る結晶性の乱れを引き続いて成長形成されるバル
ク単結晶がそのまま受け継いだ形態となるため、
成長した結晶は均質な結晶部分の範囲が著しく制
限される。従つて、実用上必要な径大寸法の単結
晶を再現性良く得ることは容易でなく生産効率が
非常に悪いというのが実情である。これらの問題
は多くの−族化合物半導体に現出する。<Prior art and its problems> Sublimation method or halogen transport method has generally been used to grow - group compound semiconductor single crystals such as ZnS and ZnSe. However, with conventional growth methods, single crystal growth Because the bulk single crystal that continues to grow and form continues to inherit the initial disordered crystallinity,
The grown crystal has a significantly limited range of homogeneous crystal parts. Therefore, the reality is that it is not easy to obtain a single crystal with a large diameter required for practical use with good reproducibility, and the production efficiency is very low. These problems appear in many − group compound semiconductors.
＜発明の目的＞
本発明は斯る点に鑑みてなされたもので、昇華
法またはハロゲン輸送法を用いて−族化合物
のバルク単結晶を気相成長させる方法において、
成長系中に配設される種結晶室と単結晶成長室を
分離し、種結晶室に予め装着配置された種結晶の
成長機構に技術的手段を駆使することによつて任
意の寸の均質な高品質バルク単結晶を成長させる
方法を提供することを目的とするものである。<Object of the invention> The present invention has been made in view of the above points, and provides a method for growing a bulk single crystal of a - group compound in a vapor phase using a sublimation method or a halogen transport method.
By separating the seed crystal chamber and single crystal growth chamber arranged in the growth system, and making full use of technical means for the growth mechanism of the seed crystal, which is pre-installed in the seed crystal chamber, we can produce homogeneous crystals of any size. The purpose of this invention is to provide a method for growing high-quality bulk single crystals.
＜発明の概要＞
上記目的を達成するため、本発明の結晶成長方
法は、予め準備された種結晶を装着したヒートシ
ンクを備えた種結晶室と種結晶の貫穿が可能な隔
壁で仕切られた単結晶成長室を具備する成長装置
を利用した単結晶成長法を特徴とするものであ
る。具体的には、種結晶を装着したヒートシンク
部より低温とな構造を持たず、ヒートシンク部と
結晶成長室までが適度な距離を隔てて設置された
成長装置を用いることによつて種結晶室で伸長し
結晶成長室に達した種結晶成長体が、その先端の
良質な小単結晶面から結晶成長室で乱れの少ない
単結晶成長を行なうものである。<Summary of the Invention> In order to achieve the above object, the crystal growth method of the present invention comprises a seed crystal chamber equipped with a heat sink equipped with a seed crystal prepared in advance, and a unit partitioned by a partition wall through which the seed crystal can penetrate. This method is characterized by a single crystal growth method using a growth apparatus equipped with a crystal growth chamber. Specifically, by using a growth device that does not have a structure where the temperature is lower than the heat sink part on which the seed crystal is attached, and in which the heat sink part and the crystal growth chamber are installed at an appropriate distance, it is possible to grow the seed crystal in the seed crystal chamber. The seed crystal growth body, which has elongated and reached the crystal growth chamber, grows a single crystal with little disturbance in the crystal growth chamber from a small single crystal face of good quality at its tip.
＜実施例＞
ZnSの沃素輸送法による単結晶成長を例にとつ
て本発明の１実施例を説明する。<Example> An example of the present invention will be described by taking as an example the single crystal growth of ZnS by the iodine transport method.
第１図は本実施例の説明に供する原理説明図で
ある。結晶成長容器１は、種結晶室２と原料室３
に貫穿孔を持つ隔壁４により分離され、原料室３
の底部には−族化合物半導体の成長用原料５
が充填されている。一方、種結晶室２にはヒート
シンク６に装着された種結晶７が配置されてい
る。この結晶成長容器１は所要の温度分布に加熱
された炉中に挿入されて種結晶７への結晶成長が
開始される。即ち、隔壁４の貫穿孔より流入する
原料５の蒸気が種結晶７上に堆積され種結晶７よ
り結晶子８が伸長して貫穿孔付近まで先細りしな
がら成長する。この先細りした結晶子８の先端は
結晶性が高く、原料室３上部の結晶成長室内で得
られる結晶の径大化成長における良質種結晶とし
て作用し、均一な高品質単結晶９の成長を可能な
らしめる。 FIG. 1 is a diagram for explaining the principle of this embodiment. The crystal growth container 1 has a seed crystal chamber 2 and a raw material chamber 3.
The raw material chamber 3 is separated by a partition wall 4 having a through hole in the chamber 3.
At the bottom of the - group compound semiconductor growth raw material 5
is filled. On the other hand, a seed crystal 7 attached to a heat sink 6 is arranged in the seed crystal chamber 2 . This crystal growth container 1 is inserted into a furnace heated to a required temperature distribution, and crystal growth into a seed crystal 7 is started. That is, the vapor of the raw material 5 flowing through the perforations in the partition wall 4 is deposited on the seed crystal 7, and the crystallites 8 extend from the seed crystal 7 and grow while tapering to the vicinity of the perforations. The tip of this tapered crystallite 8 has high crystallinity and acts as a high-quality seed crystal during the growth of the crystal to enlarge the diameter obtained in the crystal growth chamber above the raw material chamber 3, making it possible to grow a uniform high-quality single crystal 9. Get used to it.
第２図は、本発明の１実施例の説明に供する沃
素輸送法を用いたZnS結晶成長装置の要部構成図
である。 FIG. 2 is a diagram showing the main part of a ZnS crystal growth apparatus using an iodine transport method, which is used to explain one embodiment of the present invention.
石英アンプル１′は、互いに貫穿孔を介して連
通された直径数十mm、長さ数十cmの単結晶成長室
と互さ５〜30mmの種結晶室２′を有し、種結晶
７′の上方より棒状の石英ヒートシンク６′が垂設
されている。単結晶成長室の肩壁は種結晶室２′
との隔壁を構成し緩やかにわん曲している。ヒー
トシンク６′は下単にZnSの種結晶７′を装着して
いる。種結晶室２′で種結晶７′から結晶子８′が
伸長する。この結晶子８′は種結晶７′より下方へ
漸次成長するに従つて径小となり、単結晶成長室
へ向つて先尖化されながら伸びる。そして単結晶
成長室との境界隔壁の貫穿孔付近で最小径とな
る。この結晶子８′の先端から単結晶成長室で良
質のZnSバルク単結晶が成長する。種結晶質２′
に種結晶７′よりも低温部となるような構造があ
ると種結晶７′以外からも自然核発生し、複数の
種結晶を用いた成長即ち多結晶成長となるため、
種結晶７′が最低温部となるように温度制御する
ことが必要である。石英アンプル１′の底部には、
原料５′としてZnSが載置されている。上記構成
を具備する石英アンプル１′等を温度制御する成
長炉（図示せず）には必要な温度が付与されてお
り、各部の温度は600℃から1200℃の範囲で適宜
選定される。 The quartz ampoule 1' has a single crystal growth chamber with a diameter of several tens of mm and a length of several tens of centimeters, which are communicated with each other via a through hole, and a seed crystal chamber 2' with a diameter of 5 to 30 mm. A rod-shaped quartz heat sink 6' is hung vertically from above. The shoulder wall of the single crystal growth chamber is the seed crystal chamber 2'
It is gently curved and forms the bulkhead between the two. A ZnS seed crystal 7' is attached to the bottom of the heat sink 6'. Crystallites 8' extend from the seed crystal 7' in the seed crystal chamber 2'. This crystallite 8' becomes smaller in diameter as it gradually grows downward from the seed crystal 7', and extends toward the single crystal growth chamber while being pointed. The diameter reaches its minimum near the perforation of the boundary wall with the single crystal growth chamber. A high quality ZnS bulk single crystal is grown from the tip of this crystallite 8' in a single crystal growth chamber. seed crystal material 2'
If there is a structure where the temperature is lower than that of the seed crystal 7', spontaneous nucleation will occur from sources other than the seed crystal 7', resulting in growth using multiple seed crystals, that is, polycrystalline growth.
It is necessary to control the temperature so that the seed crystal 7' becomes the lowest temperature part. At the bottom of the quartz ampoule 1',
ZnS is placed as the raw material 5'. A growth furnace (not shown) for controlling the temperature of the quartz ampoule 1' having the above-mentioned structure is provided with a necessary temperature, and the temperature of each part is appropriately selected in the range of 600°C to 1200°C.
ヒートシンク６′を温度調節して種結晶７′の下
端面を最も低い温度に設定し、石英アンプル１′
を800℃程度に加熱する。加熱されたZnS原料
５′よりZnSはZnI2とS2の分子から成る蒸気とな
つて上昇し、種結晶７′下端面で冷却されて種結
晶７′面に結晶子８′が析出する。この結晶子８′
は種結晶室２′内で漸次伸長し単結晶成長室との
境界で最小径先端部を呈する。この先端面より次
の単結晶成長室でバルク状のZnS単結晶９′が成
長される。このバルクZnS単結晶９′は微小単結
晶表面より成長されたものであるため、結晶欠陥
の導入される確率もきわめて小さく良好な結晶性
を有する単結晶となる。またZnS単結晶の形状は
単結晶成長室の壁面形状に即してほぼ決定される
ため、壁面形状特に肩壁付近のわん曲形状を適宜
設定することにより任意に制御される。 Adjust the temperature of the heat sink 6' to set the lower end surface of the seed crystal 7' to the lowest temperature, and then
Heat to about 800℃. ZnS rises from the heated ZnS raw material 5' as a vapor consisting of ZnI 2 and S 2 molecules, is cooled at the lower end face of the seed crystal 7', and crystallites 8' are precipitated on the surface of the seed crystal 7'. This crystallite 8'
gradually expands within the seed crystal chamber 2' and exhibits the smallest diameter tip at the boundary with the single crystal growth chamber. A bulk ZnS single crystal 9' is grown from this tip in the next single crystal growth chamber. Since this bulk ZnS single crystal 9' is grown from the surface of a minute single crystal, the probability of introducing crystal defects is extremely small, resulting in a single crystal with good crystallinity. Further, since the shape of the ZnS single crystal is almost determined according to the wall shape of the single crystal growth chamber, it can be arbitrarily controlled by appropriately setting the wall shape, especially the curved shape near the shoulder wall.
＜発明の効果＞
以上詳説した如く本発明の製造技術を用いるこ
とにより、単結晶で伸長し結晶成長室に達した種
結晶成長体が、その先端の良質な小単結晶面から
結晶成長室で乱れの少ない単結晶成長を行うこと
が可能になるため、任意の寸法の均質な高品位バ
ルク単結晶を容易に得ることができる。<Effects of the Invention> As explained in detail above, by using the manufacturing technology of the present invention, the seed crystal growth body, which has been elongated as a single crystal and reached the crystal growth chamber, is grown in the crystal growth chamber from the high-quality small single crystal face at its tip. Since it becomes possible to grow a single crystal with less turbulence, it is possible to easily obtain a homogeneous, high-quality bulk single crystal of any size.
第１図は本発明の１実施例の説明に供する成長
装置の原理図である。第２図は本発明の１実施例
の説明に供する成長装置の要部構成図である。
１……結晶成長容器、２……種結晶室、３……
原料室、４……隔壁、５……原料、６……ヒート
シンク、７……種結晶、８……結晶子、９……単
結晶。
FIG. 1 is a principle diagram of a growth apparatus used to explain one embodiment of the present invention. FIG. 2 is a diagram showing the main part of a growth apparatus for explaining one embodiment of the present invention. 1...Crystal growth container, 2...Seed crystal chamber, 3...
Raw material chamber, 4... Partition wall, 5... Raw material, 6... Heat sink, 7... Seed crystal, 8... Crystallite, 9... Single crystal.
Claims (1)
族化合物半導体単結晶の気相成長方法において、 バルク単結晶成長用種結晶が装置配置され、該
バルク単結晶成長用種結晶が最も低温に保れた種
結晶室と、 該結晶室に適宜空間を隔てて連結された結晶成
長室の少なくとも２室を介して、 前記種結晶室で前記種結晶を伸長し、前記結晶
成長室との境界で最小径先端部をなし、かつこれ
に連結されるバルク単結晶を前記結晶成長室で成
長せしめることを特徴とする化合物半導体単結晶
の気相成長方法。[Claims] 1. Using sublimation method or halogen transport method -
In a method for vapor phase growth of group compound semiconductor single crystals, a seed crystal for bulk single crystal growth is arranged in the apparatus, a seed crystal chamber in which the seed crystal for bulk single crystal growth is kept at the lowest temperature, and an appropriate space in the crystal chamber. The seed crystal is elongated in the seed crystal chamber through at least two crystal growth chambers connected to each other with a gap between the crystal growth chambers, and the seed crystal has a minimum diameter tip at the boundary with the crystal growth chamber, and is connected to the crystal growth chamber. A method for vapor phase growth of a compound semiconductor single crystal, comprising growing a bulk single crystal in the crystal growth chamber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12672386A JPS62283897A (en) | 1986-05-30 | 1986-05-30 | Vapor growth method for compound semiconductor single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12672386A JPS62283897A (en) | 1986-05-30 | 1986-05-30 | Vapor growth method for compound semiconductor single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62283897A JPS62283897A (en) | 1987-12-09 |
| JPH0371400B2 true JPH0371400B2 (en) | 1991-11-13 |
Family
ID=14942278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12672386A Granted JPS62283897A (en) | 1986-05-30 | 1986-05-30 | Vapor growth method for compound semiconductor single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62283897A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49129694A (en) * | 1973-04-04 | 1974-12-12 | ||
| JPS6143275B2 (en) * | 1981-06-04 | 1986-09-26 | Westvako Corp |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6143275U (en) * | 1984-08-17 | 1986-03-20 | 三洋電機株式会社 | crystal growth equipment |
-
1986
- 1986-05-30 JP JP12672386A patent/JPS62283897A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49129694A (en) * | 1973-04-04 | 1974-12-12 | ||
| JPS6143275B2 (en) * | 1981-06-04 | 1986-09-26 | Westvako Corp |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62283897A (en) | 1987-12-09 |
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