JPS62172000A - Single crystal growth of ii-vi compound - Google Patents
Single crystal growth of ii-vi compoundInfo
- Publication number
- JPS62172000A JPS62172000A JP1423286A JP1423286A JPS62172000A JP S62172000 A JPS62172000 A JP S62172000A JP 1423286 A JP1423286 A JP 1423286A JP 1423286 A JP1423286 A JP 1423286A JP S62172000 A JPS62172000 A JP S62172000A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- zone
- crystal
- growth
- ampoule
- 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
- 239000013078 crystal Substances 0.000 title claims abstract description 56
- 150000001875 compounds Chemical class 0.000 title claims abstract description 15
- 239000003708 ampul Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000005092 sublimation method Methods 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 5
- 238000001947 vapour-phase growth Methods 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 8
- 239000010453 quartz Substances 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 abstract 1
- 239000005083 Zinc sulfide Substances 0.000 abstract 1
- 239000012159 carrier gas Substances 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 229910052984 zinc sulfide Inorganic materials 0.000 abstract 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000002109 crystal growth method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- -1 Zn5e Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008710 crystal-8 Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ハロゲンによる化学輸送法（ハロゲン輸送法
）あるいは昇華再結晶法（昇華法）を用いたＩＩ−ＶＩ
族化合物（ＺｎＳ、Ｚｎ５ｅ等）のバルク単結晶成長法
に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention is directed to the II-VI
This invention relates to a method for growing bulk single crystals of group compounds (ZnS, Zn5e, etc.).
（従来の技術〉
ＺｎＳ、Ｚｎ５ｅ等のＩＩ−ＶＩ族化合物は、そのエネ
ルギーバンド・ギャップが紫外から青色領域に対応する
ため、可視短波長（緑色・青色）から紫外域での光電変
換材料として有用な半導体材料であり、ＳｉＣ，ＧａＮ
等を含めてもいまだに十分に実用性のあるデバイス化が
実現していない青色発光ダイオード材料としても本質的
に高効率発光が可能である。可視発光ダイオードが家庭
電気、産業機器、情報機器等の産業上に占める重要性が
ますます増大する今日、これらの■−■族化合物の良質
結晶の成長とデバイス化の実現は極めて大きい産業上の
意味を持つ。(Prior technology) II-VI group compounds such as ZnS and Zn5e are useful as photoelectric conversion materials in the visible short wavelength (green/blue) to ultraviolet range because their energy band gap corresponds to the ultraviolet to blue region. It is a semiconductor material such as SiC, GaN
It is essentially possible to emit light with high efficiency even as a blue light emitting diode material, which has not yet been realized as a sufficiently practical device. Today, as visible light-emitting diodes are becoming more and more important in industries such as home appliances, industrial equipment, and information equipment, the growth of high-quality crystals of these ■-■ group compounds and the realization of devices will be an extremely important industrial goal. have meaning.
第２図（イ）、（ロ）に図式的に示すように、ＺｎＳ。As schematically shown in FIGS. 2(a) and 2(b), ZnS.
Ｚｎ５ｅ等の■−■族化合物のハロゲン輸送法あるいは
昇華法を用いたバルク単結晶の成長法では、従来、平坦
部とそれに続く緩やかに減少する自然温度勾配を持つ温
度分布（第２図（イ）の５）あるいは、低、高の二つの
温度Ｔ１．Ｔｔが定められた温度分布（第２図（ロ）の
５）を有する加熱炉中で、石英製の結晶成長容器（アン
プル）１中に設置された原料部分２と種結晶部分４の温
度を設定して、単結晶３を種結晶４からまたはアンプル
の先端から成長させる。なお、第２図（イ）、（ロ）は
、それぞれ、縦型加熱炉と横型加熱炉を用いる場合を示
す。In bulk single crystal growth methods using the halogen transport method or sublimation method for ■-■ group compounds such as Zn5e, conventionally, a temperature distribution with a flat area followed by a gradually decreasing natural temperature gradient (Fig. ) or 5) or two temperatures T1.), low and high. In a heating furnace having a temperature distribution with a determined Tt (5 in Figure 2 (b)), the temperature of the raw material part 2 and the seed crystal part 4 placed in a crystal growth container (ampule) 1 made of quartz is controlled. Set up, a single crystal 3 is grown from the seed crystal 4 or from the tip of the ampoule. Note that FIGS. 2(a) and 2(b) show cases in which a vertical heating furnace and a horizontal heating furnace are used, respectively.
（発明の解決しようとする問題点）
■−■族化合物のハロゲン輸送法あるいは昇華法による
単結晶成長技術の現在の水準では、成長する結晶のフロ
ントは一意的に定まらず、すなわち異なる温度の場所で
の成長が同時に進行することあるいは、異なる方位の面
」−での成長が同時に進行することがある。したがって
、成長する結晶の形状は、単結晶が得られる場合におい
ても、アンプルの形状のわずかな違いや仕込条件のわず
かな変化とそれらにより生ずるアンプル管内の対流の影
響を反映して、成長実行毎に任意の面が勝手な方向に発
達した制御されない形状を呈し、しかもこの結果として
、単結晶の寸法も最大でも１０〜１５ｍｍ程度に留まっ
ている。いいかえれば、デバイス製作用あるいは単結晶
成長基板用として用い得る水準の高品質かつ十分な寸法
の結晶を得る技術は確立されていない。例えば、エピタ
キシャル成長用基板としては、特殊な用途を除いては、
ＺｎＳ、Ｚｎ５ｅ等にとっては、不純物として作用する
元素を含むため不利なＧａＡｓ 、ＧａＰ等を用いざる
を得ないのが現状である。このことは、ＺｎＳ、Ｚｎ５
ｅ等の物性制御の上で重要な要因である高純度化、低欠
陥密度化を目指す現在のデバイス化を含めた研究開発に
おいて極めて重大な問題となっている。(Problems to be Solved by the Invention) With the current level of single crystal growth technology using the halogen transport method or sublimation method for ■-■ group compounds, the front of the growing crystal is not uniquely determined, that is, locations at different temperatures. Growth may occur at the same time, or growth may occur at the same time in different oriented planes. Therefore, even when a single crystal is obtained, the shape of the growing crystal changes with each growth run, reflecting slight differences in the shape of the ampoule, slight changes in the preparation conditions, and the effects of convection within the ampoule tube. It exhibits an uncontrolled shape in which arbitrary planes develop in arbitrary directions, and as a result, the size of the single crystal remains at the maximum of about 10 to 15 mm. In other words, no technology has been established for obtaining crystals of high quality and sufficient size that can be used for device fabrication or single crystal growth substrates. For example, as a substrate for epitaxial growth, except for special uses,
Currently, it is necessary to use GaAs, GaP, etc., which are disadvantageous for ZnS, Zn5e, etc. because they contain elements that act as impurities. This means that ZnS, Zn5
This has become an extremely important problem in current research and development, including device development, which aims to achieve high purity and low defect density, which are important factors in controlling physical properties such as e.
本発明は、」二記の点に鑑みてなされたものであり、そ
の目的は、石英アンプル中でのＩＩ−ＶＩ族化合物のハ
ロゲン輸送法および昇華法による成長法において従来方
法が有する限界と欠点を除去し、高品質の十分な寸法を
持つ形状の制御されたバルク単結晶を成長させる方法を
提供することである。The present invention has been made in view of the above two points, and its purpose is to overcome the limitations and drawbacks of conventional methods of growing II-VI group compounds in quartz ampoules by halogen transport and sublimation. It is an object of the present invention to provide a method for growing bulk single crystals of high quality, of sufficient size, and of controlled shape.
（問題点を解決するための手段）
本発明に係る■−■族化合物の単結晶は、ハロゲン輸送
法あるいは昇華法を用いた気相成長法において、結晶成
長フロントが位置するように温度を制御し、かつ所定の
温度勾配に制御した狭い結晶成長ゾーン中に、原料を一
端に配置した結晶成長用アンプルを所定の牽引速度に制
御して移動させることを特徴とする。(Means for Solving the Problems) The single crystal of the ■-■ group compound according to the present invention is produced by controlling the temperature so that the crystal growth front is located in a vapor phase growth method using a halogen transport method or a sublimation method. The present invention is characterized in that a crystal growth ampoule with a raw material placed at one end is moved at a predetermined pulling speed into a narrow crystal growth zone controlled to a predetermined temperature gradient.
（作 用）
本発明の単結晶成長法の特徴は、ハロゲン輸送法および
昇華法を用いて■−■族化合物のバルク単結晶を成長さ
せる際、加熱炉内の温度分布において結晶成長化部分を
急勾配を有する温度傾斜とすることおよび結晶成長アン
プルを一定速度で牽引することである。さらに具体的に
は、石英アンプル中に設置したもしくは自然核発生によ
り生成した種結晶から成長する際に、小さな温度差でし
かも急勾配を持つ温度傾斜部を利用することにより、温
度分布（傾斜部）の一点即ちほぼ等温と見なせる一定の
平面内のみでの結晶の成長が可能であるようにした上で
、一定のあるいは段階的に変化させた速度でアンプルを
移動させることにより結晶成長フロントを上記の一定温
度の点を通過させて、温度分布あるいはアンプル形状等
に依存せず一定の形で定常的に単結晶化させることによ
って、はぼアンプルの断面状の切断面を持つ任意の長さ
のバルク単結晶を得る成長法を具現させたことにある。(Function) A feature of the single crystal growth method of the present invention is that when growing a bulk single crystal of a ■-■ group compound using a halogen transport method and a sublimation method, the crystal growth portion is controlled in the temperature distribution in the heating furnace. The two methods are to provide a steep temperature gradient and to pull the crystal growth ampoule at a constant speed. More specifically, when growing from a seed crystal placed in a quartz ampoule or generated by natural nucleation, the temperature distribution (slope part ), that is, within a fixed plane that can be considered almost isothermal, and then by moving the ampoule at a fixed or stepwise speed, the crystal growth front can be grown as described above. By passing through a constant temperature point and steadily forming a single crystal in a constant shape regardless of temperature distribution or ampoule shape, we can create crystals of arbitrary length with a cross-sectional surface similar to that of the ampoule. The goal is to realize a growth method for obtaining bulk single crystals.
（実施例） 以下、本発明の実施例を第１図によって説明する。(Example) Embodiments of the present invention will be described below with reference to FIG.
石英製の結晶成長容器（アンプル）６内の両端に、原料
７および種結晶９を充填する（ハロゲン輸送法では、輸
送ガスも封入する。）。縦型加熱炉内に高温部（温度Ｔ
、″）１１、低温部（温度Ｔ、°）および中間の温度傾
斜部Ｉ３からなる温度分布１０を実現させる。温度傾斜
部１３の温度は、結晶が成長する温度に設定する。いい
かえれば、温度傾斜部１３は結晶成長ゾーンである。Ｔ
ｔ’とＴ Ｉ’との温度差へＴは小さくし、しかも、温
度傾斜部１３では約り℃／ｃｍ以上の急勾配へＴ／ΔＸ
を持たせる。A raw material 7 and a seed crystal 9 are filled at both ends of a crystal growth container (ampule) 6 made of quartz (in the halogen transport method, a transport gas is also enclosed). There is a high temperature section (temperature T
,'') 11, a temperature distribution 10 consisting of a low temperature part (temperature T, °) and an intermediate temperature gradient part I3 is realized.The temperature of the temperature gradient part 13 is set to a temperature at which crystals grow.In other words, the temperature The inclined portion 13 is a crystal growth zone.T
The temperature difference between t' and T I' is made small, and T/ΔX is made so that the temperature gradient part 13 has a steep slope of approximately ℃/cm or more.
to have.
そして、アンプル６を、高温部１０に挿入する。Then, the ampoule 6 is inserted into the high temperature section 10.
次に、一定のあるいは段階的に変化させた０、１〜２０
ｍｍ／ｄａｙの一定牽引速度■でアンプル６を上方向へ
牽引して移動させる。種結晶９が温度傾斜部１３内を上
方に移動するにつれ、温度傾斜部１３の一点１４すなわ
ちほぼ等温とみなせる一定の平面内で結晶が成長してい
く。この点が結晶成長フロント８Ａになる。換言すれば
、結晶成長フロント８Ａが温度傾斜部１３の一点１４に
常時位置するように制御する。このようにして、アンプ
ル６を上方向に移動させていくと、はぼアンプル６の内
周面の外形を有し、任意の長さを有するバルク単結晶８
が成長していく。Next, a constant or stepwise change of 0, 1 to 20
The ampoule 6 is pulled upward at a constant pulling speed of mm/day. As the seed crystal 9 moves upward within the temperature gradient section 13, the crystal grows at a point 14 of the temperature gradient section 13, that is, within a fixed plane that can be considered to be approximately isothermal. This point becomes the crystal growth front 8A. In other words, the crystal growth front 8A is controlled to be always located at one point 14 of the temperature gradient section 13. In this way, as the ampoule 6 is moved upward, a bulk single crystal 8 having the outer shape of the inner circumferential surface of the ampoule 6 and having an arbitrary length.
is growing.
本成長法においては、加熱炉が垂直配置の場合において
も、水平配置の場合においても、成長結晶の制御性にお
いて同等の効果と生産性を有する。This growth method has the same effect and productivity in terms of controllability of grown crystals whether the heating furnace is vertically arranged or horizontally arranged.
また、アンプルと炉は相対的にいずれかを移動させる。Also, the ampoule and the furnace are moved relative to each other.
アンプル口径およびアンプル長を実用的に任意に選び、
充填原料を所望の量として温度勾配とアンプル牽引速度
に所定の値に設定することにより、一定の定常的成長条
件下で任意の口径と長さを有する高品位かつ均質なＺｎ
Ｓ、Ｚｎ５ｅ等の■−■族化合物バルク単結晶を高い生
産性をもって成長させることができる。Select the ampoule diameter and ampoule length as desired for practical purposes.
By setting the temperature gradient and ampoule drawing speed to predetermined values with the desired amount of filling material, high-grade and homogeneous Zn with arbitrary diameter and length can be produced under constant steady growth conditions.
It is possible to grow bulk single crystals of ■-■ group compounds such as S and Zn5e with high productivity.
（発明の効果）
第１図
本発明により、ＩＩ−ＶＩ族化合物のデバイス用結晶お
よびエピタキシャル基板用結晶を供給することが可能と
なる。(Effects of the Invention) FIG. 1 The present invention makes it possible to supply device crystals and epitaxial substrate crystals of II-VI group compounds.
第１図は、本発明のハロゲン輸送法あるいは昇華法によ
る成長法の概略図である。
第２図（イ）、（ロ）は、それぞれ、ハロゲン輸送法お
よび昇華法によＩ）結晶成長させる場合に従来用いられ
てきた成長法の概略図である。
６・・・結晶成長用アンプル、 ７・・・原料、訃
・・成長結晶、９・・・種結晶、１０・・・温度分布、
１１・・・高温部、１２・・・低温部、１３・・・温度
傾斜部。FIG. 1 is a schematic diagram of the growth method using the halogen transport method or sublimation method of the present invention. FIGS. 2(a) and 2(b) are schematic diagrams of the conventional growth methods used in I) crystal growth by halogen transport method and sublimation method, respectively. 6... Ampoule for crystal growth, 7... Raw material, Grain... Growing crystal, 9... Seed crystal, 10... Temperature distribution,
11...High temperature section, 12...Low temperature section, 13...Temperature gradient section.
Claims (1)
昇華法を用いた気相成長法において、結晶成長フロント
が位置するように温度を制御し、かつ所定の温度勾配に
制御した狭い結晶成長ゾーン中に、原料を一端に配置し
た結晶成長用アンプルを所定の牽引速度に制御して移動
させることを特徴とするII−VI族化合物の単結晶成長法
。(1) In a vapor phase growth method using a halogen transport method or a sublimation method for II-VI group compound single crystals, narrow crystal growth is performed by controlling the temperature so that the crystal growth front is located and controlling it to a predetermined temperature gradient. A method for growing a single crystal of a Group II-VI compound, which comprises moving a crystal growth ampoule with a raw material placed at one end in a zone while controlling it at a predetermined traction speed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1423286A JPS62172000A (en) | 1986-01-24 | 1986-01-24 | Single crystal growth of ii-vi compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1423286A JPS62172000A (en) | 1986-01-24 | 1986-01-24 | Single crystal growth of ii-vi compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62172000A true JPS62172000A (en) | 1987-07-28 |
| JPH0369880B2 JPH0369880B2 (en) | 1991-11-05 |
Family
ID=11855325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1423286A Granted JPS62172000A (en) | 1986-01-24 | 1986-01-24 | Single crystal growth of ii-vi compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62172000A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101922041A (en) * | 2009-06-10 | 2010-12-22 | 硅电子股份公司 | The drawing method of silicon single-crystal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49129694A (en) * | 1973-04-04 | 1974-12-12 | ||
| JPS59164695A (en) * | 1983-03-10 | 1984-09-17 | Matsushita Electric Ind Co Ltd | Preparation of single crystal |
-
1986
- 1986-01-24 JP JP1423286A patent/JPS62172000A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49129694A (en) * | 1973-04-04 | 1974-12-12 | ||
| JPS59164695A (en) * | 1983-03-10 | 1984-09-17 | Matsushita Electric Ind Co Ltd | Preparation of single crystal |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101922041A (en) * | 2009-06-10 | 2010-12-22 | 硅电子股份公司 | The drawing method of silicon single-crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0369880B2 (en) | 1991-11-05 |
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