JPH01239099A - Production of bulk single crystal of ii-vi compound - Google Patents
Production of bulk single crystal of ii-vi compoundInfo
- Publication number
- JPH01239099A JPH01239099A JP6487888A JP6487888A JPH01239099A JP H01239099 A JPH01239099 A JP H01239099A JP 6487888 A JP6487888 A JP 6487888A JP 6487888 A JP6487888 A JP 6487888A JP H01239099 A JPH01239099 A JP H01239099A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- sealed tube
- iodine
- compound
- temperature
- 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 85
- 150000001875 compounds Chemical class 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000011630 iodine Substances 0.000 claims abstract description 23
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 23
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 abstract description 20
- 239000010453 quartz Substances 0.000 abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 13
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 150000004678 hydrides Chemical class 0.000 abstract description 3
- 229910021476 group 6 element Inorganic materials 0.000 abstract 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 abstract 1
- 239000003708 ampul Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 229910052984 zinc sulfide Inorganic materials 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- -1 ZnS Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000005092 sublimation method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007740 vapor deposition Methods 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、■−■族化合物のバルク単結晶の製造法に関
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a bulk single crystal of a ■-■ group compound.
ＺｎＳ、 Ｚｎ５ｅ％ＣｄＨｇＴｅ等の■−■族化合物
半導体はＳｉ等の■族又はＧａ Ａｓ等のＩＩＩ−Ｖ族
化合物半導体では得られない青色発光ダイオード、赤外
線検出素子等の機能が得られることが期待されている。■-■ group compound semiconductors such as ZnS, Zn5e%CdHgTe, etc. are expected to provide functions such as blue light emitting diodes and infrared detection elements that cannot be obtained with ■-group compound semiconductors such as Si or III-V group compound semiconductors such as GaAs. has been done.
またこれら■−■族単結晶の中には、その光学的特性を
生かしたいわゆる赤外線用窓材としての利用されている
ものもある。Furthermore, some of these ■-■ group single crystals are utilized as so-called infrared window materials by making use of their optical properties.
このよりな■−■族化合物のバルク単結晶は従来、気相
又は液相から昇華法、高圧溶融法等種々の方法で得られ
ることが知られているが、ヨウ素を輸送剤として用いる
ヨウ素輸送法が挙げられる。ヨウ素輸送法には昇華法に
比べ低温成長が可能であるため格子欠陥濃度が低減され
、また、簡単な装置で単結晶が製造可能であるという利
点がある。It is known that bulk single crystals of these solid ■-■ group compounds can be obtained from the gas phase or liquid phase by various methods such as sublimation method and high pressure melting method. One example is the law. Compared to the sublimation method, the iodine transport method has the advantage that low-temperature growth is possible, so the lattice defect concentration is reduced, and single crystals can be produced using simple equipment.
このようなヨウ素輸送法においては、従来数喘角の単結
晶を種結晶として用いて、封管内で単結晶を成長させる
方法が採られている。しかし、このヨウ素輸送法で得ら
れる単結晶は少からずアメ色に着色しており、また結晶
の欠陥の尺度を表わすエッチピット密度も３〜りＸ１０
’ｃｒｒＬ−”と高いものであった。そして、赤外線窓
材にはかかる結晶は使用不可能であり、従来は薄膜形成
手法である蒸着、分子線エピタキシャル法（ＭＢＥ）、
有機金属化学気相法（ＭＯＣＶＤ）等の手段で数瓢厚さ
にも及ぶ厚膜を作成するという極めて非能率な方法がと
られていた。In such an iodine transport method, a method has conventionally been adopted in which a single crystal with a diameter of several angles is used as a seed crystal and the single crystal is grown in a sealed tube. However, the single crystals obtained by this iodine transport method are colored amber in color, and the etch pit density, which is a measure of crystal defects, is 3 to 10.
'crrL-' and such crystals cannot be used for infrared window materials, and conventional thin film forming methods such as vapor deposition, molecular beam epitaxial method (MBE),
An extremely inefficient method has been used to create a thick film several thicknesses thick using methods such as metal organic chemical vapor deposition (MOCVD).
また、封管内への種結晶の取υ付けは困難であり、また
原料の■−■族化合物の粉末が種結晶に付着し、多結晶
成長が生じやすくなる等成長過程が複雑になり、工業的
応用には適さない。In addition, it is difficult to attach a seed crystal inside a sealed tube, and the powder of the ■-■ group compound of the raw material adheres to the seed crystal, making the growth process more complicated, such as making polycrystalline growth more likely to occur. Not suitable for practical applications.
〔発明が解決しようとする課題〕
そこで、本発明者は、種結晶を用いないで■−■族化合
物のバルク単結晶を得、且つ得られる単結晶の着色を減
少させ、エッチピット密度を小さくすることによって、
良品質半導体基板として使用可能とするとともに赤外線
窓材としても使用可能な高品質な■−■族化合物のバル
ク単結晶を得るため鋭意検討した結果、本発明に到達し
た。[Problems to be Solved by the Invention] Therefore, the present inventor obtained a bulk single crystal of a ■-■ group compound without using a seed crystal, and also reduced the coloring of the obtained single crystal and reduced the etch pit density. By,
The present invention has been achieved as a result of intensive studies to obtain a bulk single crystal of a high-quality 1-2 group compound that can be used as a high-quality semiconductor substrate and also as an infrared window material.
即ち、本発明の要旨は、■−■族化合物のバルク単結晶
を、一方が円錘状である封管内でヨウ素輸送法により製
造する方法において、封管の長手方向の中心軸を含む断
面内の該円錘の頂角がｊ〜３０である封管を用いて種結
晶を使用しｋいでバルク単結晶を成長させることを特徴
とするＩＩ−■族化合物のバルク単結晶の製造法及び該
製造法において、原料の■−■族化合物を７００℃以上
１０００℃未満の温度において■族水累化物で前処理
することを特徴とする■−■族化合物のバルク単結晶の
製造法に存する。That is, the gist of the present invention is to provide a method for producing a bulk single crystal of a ■-■ group compound by an iodine transport method in a sealed tube, one of which is conical. A method for producing a bulk single crystal of a group II-■ compound, characterized in that the bulk single crystal is grown at k using a seed crystal using a sealed tube whose cone has an apex angle of j to 30; The present invention relates to a method for producing a bulk single crystal of a ■-■ group compound, characterized in that the raw material ■-■ group compound is pretreated with a group-■ water complex at a temperature of 700°C or higher and less than 1000°C.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明においては、■−■族化合物のバルク単結晶を得
る方法として、ヨウ素（工２）を輸送剤として用い、封
管内の高温側で■−■族化合物原料とヨウ素を反応させ
て揮発性の化合物とし、これを低温側単結晶成長領域ま
で輸送して単結晶を成長させる、いわゆるヨウ素輸送法
が用いられる。In the present invention, as a method for obtaining a bulk single crystal of a ■-■ group compound, iodine (Process 2) is used as a transport agent, and the raw material of the ■-■ group compound is reacted with iodine on the high temperature side in a sealed tube to release volatile The so-called iodine transport method is used, in which the compound is transported to a low-temperature side single crystal growth region to grow a single crystal.
目的とする■−■族化合物の単結晶としては、ＺｎＳ、
Ｚｎ５ｅ％ＺｎＴｅ％ＣａＳ％ＣｄＴｅ、 ＣｄＨｇ
Ｔｅ等の単結晶が挙げられる。The target single crystal of the ■-■ group compound is ZnS,
Zn5e%ZnTe%CaS%CdTe, CdHg
Examples include single crystals such as Te.
単結晶を得るための原料としては、それぞれの高純度の
化合物、即ちＺｎＳ 、 Ｚｎ５ｅ ％ＣｄＳ ５Ｃｄ
Ｔｅ 、 ＣｄＨｇＴｅ等の高純度粉末又はペレットが
用いられる。これら原料化合物は１．２Ｎ、 ＪＮ程度
の純度のものでも使用できるが、好ましくは！Ｎ％６Ｎ
の純度のものが用いられる。As raw materials for obtaining single crystals, the respective high purity compounds, namely ZnS, Zn5e%CdS5Cd
High purity powder or pellets of Te, CdHgTe, etc. are used. These raw material compounds can be used even if they have a purity of about 1.2N or JN, but preferably! N%6N
purity is used.
ヨウ素はできるだけ試薬グレード以上の高純度のものが
望ましく、ヨウ素の量は封管の容量、単結晶成長時の封
管の温度差、■−■族化合物の食等により適宜定められ
るが、通常、封管の内容積／ｃｃ当り０．１〜１０ｍｇ
であり、単結晶の結晶性と単結晶中へのヨウ素のドーピ
ング量との関係から、内容積／ＣＣ当りｏ３〜２■が好
ましい。It is desirable that iodine be as pure as possible, at least reagent grade, and the amount of iodine is appropriately determined depending on the capacity of the sealed tube, the temperature difference in the sealed tube during single crystal growth, the consumption of ■-■ group compounds, etc., but usually, 0.1 to 10 mg per cc of inner volume of sealed tube
From the relationship between the crystallinity of the single crystal and the amount of iodine doped into the single crystal, it is preferable that the internal volume/CC be o3 to 2.
本発明においては、通常、脱水と不純物の除去のために
、原料の■−■族化合物を真空中、又は高純度水素気流
中、高純度アルゴン等の不活性ガス気流中、あるいは高
純度■原水素化物ガス気流中で加熱処理する。■原水素
化物としては、硫化水素、セレン化水素等が用いられ、
またこれらの混合物を用いるξともできる。但し、水（
Ｈ２Ｏ）は除かれる。これらの中で硫化水素が特に好適
に用いられる。In the present invention, in order to dehydrate and remove impurities, the raw material (■-■ group compound) is usually stored in vacuum, in a stream of high-purity hydrogen, in a stream of inert gas such as high-purity argon, or in a stream of high-purity (2) raw material. Heat treatment in a hydride gas stream. ■Hydrogen sulfide, hydrogen selenide, etc. are used as raw hydrides.
It is also possible to use a mixture of these as ξ. However, water (
H2O) is removed. Among these, hydrogen sulfide is particularly preferably used.
加熱処理に用いるガスは、できるだけ高純度であること
が好ましく、特に■−■族化合物の加水分解や酸化を防
ぐためＨ２Ｏ及び０２の混入を防止する必要がちり、そ
れぞれ／ ｐＩ）ｍ以下、好ましくは０．／ ｐｐｍ以
下の濃度にするのが望ましい。必要に応じて、これら不
純物を除去する工程を設けるのが好ましい。It is preferable that the gas used for the heat treatment has as high a purity as possible, and in particular, it is necessary to prevent the contamination of H2O and 02 to prevent hydrolysis and oxidation of the ■-■ group compounds. is 0. It is desirable that the concentration be less than /ppm. It is preferable to provide a step for removing these impurities, if necessary.
加熱処理は、■−■族化合物の原料粉末又は小粒塊、ペ
レット等を処理容器に入れ、容器内を／ ０−３’ｐ□
ｒｒ以下に一旦排気した後、前記ガスを導入し、このガ
スを流通しながら所定の温度まで昇温し、必要に応じて
その状態を保持することによりおこなわれる。For heat treatment, the raw material powder, small lumps, pellets, etc. of the ■-■ group compound are placed in a processing container, and the inside of the container is heated to / 0-3'p□.
This is carried out by once evacuation to below rr, then introducing the gas, raising the temperature to a predetermined temperature while circulating the gas, and maintaining that state as necessary.
処理温度は、通常７００℃以上 １０００℃未満、好ま
しくはｒｓｏ℃〜９００℃の範囲から選ばれる。昇温は
、急激に昇温しても段階的に昇温しでもよく、高温での
保持時間は／時間程度から、２ψ時間程度の範囲から適
宜選ばれる。また、冷却も前記ガス気流中でおこなわれ
、急冷でも除冷でも良い。The treatment temperature is usually selected from the range of 700°C or more and less than 1000°C, preferably from rso°C to 900°C. The temperature may be raised rapidly or in stages, and the holding time at the high temperature is appropriately selected from the range of about 1 hour to about 2ψ hours. Further, cooling is also performed in the gas flow, and may be rapid cooling or slow cooling.
室温まで冷却した後は、原料の■−■族化合物は高純度
■施水素化物（Ｉ２０は除く）ガス又は不活性ガス中に
保管されるのが好ましいが、単結晶成長工程へ移すため
に短時間空気中で取扱っても差しつかえない。After cooling to room temperature, the raw material ■-■ group compounds are preferably stored in high-purity ■hydrogenide (excluding I20) gas or inert gas, but are briefly stored in order to be transferred to the single crystal growth process. It may be handled in air for hours.
また、該加熱処理の後冷却せずにそのまま単結晶成長工
程に移してもよい。Alternatively, the heat treatment may be directly transferred to the single crystal growth step without being cooled.
加熱処理をおこなう容器は、通常石英製のものが用いら
れるが、■−■族化合物等と反応しないものであればよ
く、セラミックコーティングされた容器等も用いること
ができる。また、該処理容器をその！ま単結晶成長時の
封管として用いることもできるが、この場合原料粉末の
飛散等により容器内壁が汚れると単結晶成長時に多結晶
化しやすいので注意を要する。The container used for the heat treatment is usually made of quartz, but any container may be used as long as it does not react with the ■-■ group compounds, and ceramic-coated containers can also be used. In addition, the processing container is the same! It can also be used as a sealed tube during single crystal growth, but in this case care must be taken because if the inner wall of the container becomes dirty due to scattering of raw material powder, polycrystallization is likely to occur during single crystal growth.
特に、該加熱処理を■施水素化物を用いておこなうと、
着色がなくエッチビット密度の小さい高品質のバルク単
結晶が得られるので好ましい。In particular, when the heat treatment is performed using a hydrogenated product,
This is preferable because a high quality bulk single crystal with no coloring and a low etch bit density can be obtained.
このように加熱処理された■−■族化合物をヨ、つ素（
Ｉ２）とともに石英製容器に真空封入し、単結晶成長用
封管とする。The heat-treated ■-■ group compound is treated with iodine (
It is vacuum sealed in a quartz container together with I2) to form a sealed tube for single crystal growth.
本発明においては、単結晶成長用封管として一端が円錘
状である封管を用いるが、該封管の長手方向の中心軸を
含む断面内の該円錘の頂角が５〜３０度であることが必
要である。この角度がｊ度より小さいと小さな結晶しか
得られず、また３０度より大きいと多核発生により多結
晶化してしまう。In the present invention, a sealed tube having a conical end at one end is used as the sealed tube for single crystal growth, and the apex angle of the cone in the cross section including the central axis in the longitudinal direction of the sealed tube is 5 to 30 degrees. It is necessary that If this angle is smaller than j degrees, only small crystals will be obtained, and if it is larger than 30 degrees, polycrystals will occur due to multinucleation.
第７図に本発明で用いられる単結晶成長用封管の一例を
示した。先端の最も細い部分の角度（第１図中θ）が５
〜３０度であれば、第１図（ｂ）および（ｃ）のように
段階的に先端が細くなっていてもよい。但し、この場合
、第１図中θ′は通常６０度以下であることが好ましい
。また、第１図（ｄ）のように、途中にくびれがある場
合は、縦型で単結晶を成長させた場合に結晶が落下しに
くいという利点がある。FIG. 7 shows an example of a sealed tube for single crystal growth used in the present invention. The angle of the thinnest part of the tip (θ in Figure 1) is 5
As long as the angle is 30 degrees, the tip may be gradually tapered as shown in FIGS. 1(b) and 1(c). However, in this case, it is preferable that θ' in FIG. 1 is usually 60 degrees or less. Further, as shown in FIG. 1(d), when there is a constriction in the middle, there is an advantage that the crystal is less likely to fall when the single crystal is grown vertically.
封管の製造方法としては、一端がこのような円錘状をし
た石英管に■−■族化合物原料及びヨウ素を入れた後、
他端を通常の方法で真空下封じ切ってもよいし、■−■
族化合物原料及びヨウ素を通常の石英管に入れた後、他
端をこのような形状に真空下封じ切ってもよい。The method for manufacturing the sealed tube is as follows: After putting the ■-■ group compound raw material and iodine into a quartz tube with one end shaped like a cone,
You can seal the other end under vacuum in the usual way, or
After putting the group compound raw material and iodine into a normal quartz tube, the other end may be sealed in such a shape under vacuum.
本発明においては、このような特定の形状をした単結晶
成長用封管を用いることにより、種結晶を用いなくても
単結晶を成長させることができる。In the present invention, by using a sealed tube for single crystal growth having such a specific shape, a single crystal can be grown without using a seed crystal.
単結晶成長方法としては横型と縦型があるが、そのどち
らの方法を用いてもよく、また温度制御方式としてはグ
ラデイエンドフリーズ方式、炉内封管移動方式、固定温
度差方式等があるが、そのいずれの方式を用いてもよい
。There are two types of single crystal growth methods: horizontal and vertical, and either method may be used. Temperature control methods include the gradient end freeze method, the sealed tube movement method within the furnace, and the fixed temperature difference method. However, either method may be used.
封管の高温側（原料部）の温度は、通常、１００〜９０
０℃、好ましくはｒｐｏ ５−ｒｔ。The temperature on the high temperature side (raw material part) of the sealed tube is usually between 100 and 90°C.
0°C, preferably rpo 5-rt.
℃の範囲から選ばれる。また、低温側単結晶成長部の温
度は、高温側の温度よりも／〜／２０℃程度低い温度か
ら適宜選ばれる。例えば、原料粉末を真空中で加熱処理
した場合は７００℃程度低い温度、原料粉末を硫化水素
気流中で加熱処理した場合は７〜３０℃低込温度とする
のが好ましい。Selected from the range of °C. Further, the temperature of the single crystal growth part on the low temperature side is appropriately selected from a temperature that is about /20°C lower than the temperature on the high temperature side. For example, when the raw material powder is heat-treated in a vacuum, the temperature is preferably about 700°C lower, and when the raw material powder is heat-treated in a hydrogen sulfide stream, the temperature is preferably lowered by 7 to 30°C.
また、ヨウ素による輸送を定常的におこない、均質な結
晶を得るために高温側と低温側の温度差は厳密に制御さ
れなくてはならない。Furthermore, the temperature difference between the high-temperature side and the low-temperature side must be strictly controlled in order to constantly transport iodine and obtain homogeneous crystals.
単結晶成長には、通常、２〜３週間を要するが、場合に
よっては弘週間を越えることもある。Single crystal growth usually takes 2 to 3 weeks, but in some cases it may take more than a week.
本発明によって得られる■−■族のバルク単結晶は大き
さが約／ ｃｒｄと大きく、透明な立方晶型単結晶であ
る。The bulk single crystal of the 1-2 group obtained by the present invention has a large size of about / crd and is a transparent cubic type single crystal.
また、本発明で得られるバルク単結晶はヨウ素が自然ド
ープされておりｎ型半導体となっている。Further, the bulk single crystal obtained by the present invention is naturally doped with iodine and becomes an n-type semiconductor.
以下、実施例により本発明の詳細な説明するが、本発明
はその要旨を越えない限り実施例によυ限定されるもの
ではない。Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to the Examples unless the gist thereof is exceeded.
実施例／
高純度ＺｎＳ粉末（化成オプトニクス■製）を１０
Ｔｏｒｒの減圧下、２弘時間真空焼結した。Example / High purity ZnS powder (manufactured by Kasei Optonics ■)
Vacuum sintering was carried out for 2 hours under reduced pressure of Torr.
内径、２０Ｗｎの石英アンプルにｒ２のＺｎＳ原料粉末
と３０ηのヨウ素を入れ、／ ０＝ Ｔｏｒｒの減圧下
、長さ７（１ｍのところで封じ切り角度ｉｓ度で熔封し
た。内容積は２２ＣＣとなった。このアンプルを縦型電
気炉中に固定し、原料部（底部）を７００℃、単結晶成
長部（上部）をＪ′！０℃としてｌλ時間逆成長による
クリーニングを行った後、原料部（底部）温度をざＳＯ
℃、単結晶成長部（上部）温度を７ｊＯ℃として２０日
間保持して硫化亜鉛のバルク単結晶を成長させた。第２
図に単結晶の成長プログラムを示した。ZnS raw powder of r2 and iodine of 30η were placed in a quartz ampoule with an inner diameter of 20 Wn, and the mixture was melted under reduced pressure of / 0 = Torr at a sealing angle of 7 degrees (1 m).The internal volume was 22 CC. This ampoule was fixed in a vertical electric furnace, and the raw material part (bottom) was cleaned at 700°C and the single crystal growth part (top) by reverse growth for lλ hours at J'!0°C. (Bottom) Temperature SO
℃, and the temperature of the single crystal growth part (upper part) was kept at 7JO ℃ for 20 days to grow a bulk single crystal of zinc sulfide. Second
The figure shows the single crystal growth program.
冷却後アンプルを割って７．Ｏｃｒ／ｌ大の透明な単結
晶を得た。第３図は得られた単結晶の図である。After cooling, break the ampoule and 7. A transparent single crystal of Ocr/l size was obtained. FIG. 3 is a diagram of the obtained single crystal.
得られた単結晶は完全な立方晶系単結晶であった。The obtained single crystal was a perfect cubic single crystal.
実施例２
高純度ＺｎＳ粉末（化成オプトニクス■製）、２０？を
石英製ボートに採り、横型電気炉中に設置した内径ｒｏ
ｒａｎ、長さｊｏｏｒｕｎの石英管中に入れた。石英管
を１０ Ｔｏｒｒまで減圧した後、高純度硫化水素ガ
ス（日本酸素■製）を１０ＣＣ／分で石英管の一端から
流入し、他端より外部へ放出しながら、石英管を１時間
かけてｒｒ。Example 2 High purity ZnS powder (manufactured by Kasei Optonics ■), 20? was taken in a quartz boat and installed in a horizontal electric furnace.
The sample was placed in a quartz tube with a length of 1.5 mm. After reducing the pressure in the quartz tube to 10 Torr, high-purity hydrogen sulfide gas (manufactured by Nippon Sanso) was introduced at 10 CC/min from one end of the quartz tube and released from the other end, while the quartz tube was heated for 1 hour. rr.
℃に昇温し、ｒｓｏ℃に保持した状態で３時間放置した
。硫化水素の流量を１０ｔｘ／分に保持した状態で約２
時間放冷した。放冷後、直ちに？？秤量して、／≠■の
ヨウ素とともに内径／１＝ｒｕ＋の石英アンプルに移し
た。石英アンプルを約１０ Ｔｒ）ｒｒに減圧しなが
ら、アンプルの封じ切り角度が約２０度になるように長
さ７ｃｒｎのところで熔封した。内容積は約／≠Ｃとな
った。The temperature was raised to 0.degree. C. and kept at rso.degree. C. for 3 hours. Approximately 2 with the flow rate of hydrogen sulfide maintained at 10 tx/min.
It was left to cool for an hour. Immediately after cooling? ? It was weighed and transferred to a quartz ampoule with an inner diameter of /1=ru+ along with iodine of /≠■. While reducing the pressure of the quartz ampoule to about 10 Tr) rr, the ampule was sealed at a length of 7 crn so that the sealing angle of the ampoule was about 20 degrees. The internal volume was approximately /≠C.
このアンプルを縦型電気炉中に固定し、原料部（底部）
を７００℃、単結晶成長部（上部）を１ｊＯ℃として、
７．２時間逆成長によるクリーニングを行った後、原料
部♂ｊＯ℃、単結晶成長部を♂３０℃として一２０日間
保持して硫化亜鉛のバルク単結晶を成長させた。冷却後
アンプルを割って／、ｊｃ４犬の着色のない透明な立方
晶系単結晶を得た。This ampoule is fixed in a vertical electric furnace, and the raw material part (bottom part)
is 700℃, the single crystal growth part (upper part) is 1jO℃,
After cleaning by reverse growth for 7.2 hours, the raw material part was kept at ♂jO°C and the single crystal growth part was kept at ♂30°C for 120 days to grow a bulk single crystal of zinc sulfide. After cooling, the ampoule was broken to obtain uncolored, transparent cubic single crystals of JC4.
得られた結晶の（／／／ ）面を沸騰水酸化ナトリウム
２ｊ％水溶液中で１分間エツチングした後、表面の状態
を光学顕微鏡で観察した。エッチビット密度はＡ、Ｏ×
１０ｃｍ であった。The (///) face of the obtained crystal was etched for 1 minute in a boiling 2J% aqueous solution of sodium hydroxide, and then the state of the surface was observed with an optical microscope. Etch bit density is A, O×
It was 10 cm.
本発明によると、種結晶を用いなくてもヨウ素輸送法に
より、容易に大型で高品質の■−■族化合物のバルク単
結晶を得ることができる。According to the present invention, large-sized, high-quality bulk single crystals of group 1-2 compounds can be easily obtained by the iodine transport method without using seed crystals.
第７図は、本発明で用いる単結晶成長用封管の一例・を
示した断面図（封管の長手方向の中心軸を含む断面図）
である。
第２図は、実施例／の単結晶の成長プログラムを示した
図でちる。Ａは原料部、Ｂは単結晶成長部をそれぞれ示
す。
第３図は、実施例／で得られた単結晶を示した図である
。
出 願 人 三菱化成工業株式会社
代 理 人 弁理士 良否用 −（ほか１名）
英）二
チ２図FIG. 7 is a sectional view showing an example of a sealed tube for single crystal growth used in the present invention (a sectional view including the central axis in the longitudinal direction of the sealed tube)
It is. FIG. 2 is a diagram showing a single crystal growth program of Example/. A indicates a raw material section, and B indicates a single crystal growth section. FIG. 3 is a diagram showing a single crystal obtained in Example/. Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent attorney - (1 other person) English) Figure 2
Claims (2)
である封管内でヨウ素輸送法により製造する方法におい
て、封管の長手方向の中心軸を含む断面内の該円錘の頂
角が５〜３０度である封管を用いて種結晶を使用しない
でバルク単結晶を成長させることを特徴とするII−VI族
化合物のバルク単結晶の製造法。(1) In a method for producing a bulk single crystal of a II-VI group compound by the iodine transport method in a sealed tube having a conical shape at one end, 1. A method for producing a bulk single crystal of a II-VI compound, the method comprising growing a bulk single crystal using a sealed tube with an apex angle of 5 to 30 degrees without using a seed crystal.
より製造する方法において、II−VI族化合物を７００℃
以上１０００℃未満の温度においてVI族化合物で処理し
た後、一端が円錘状である封管であり、該封管の長定方
向の中心軸を含む断面内の該円錘の頂角が５〜３０度で
ある封管を用いて、種結晶を使用しないでバルク単結晶
を成長させることを特徴とするII−VI族化合物のバルク
単結晶の製造法。(2) In a method for producing a bulk single crystal of a II-VI group compound by the iodine transport method, the II-VI group compound is heated to 700°C.
After being treated with a Group VI compound at a temperature above 1000°C, the sealed tube has a conical shape at one end, and the apex angle of the cone in the cross section including the central axis in the longitudinal direction of the sealed tube is 5. 1. A method for producing a bulk single crystal of a II-VI compound, comprising growing a bulk single crystal using a sealed tube at a temperature of ~30 degrees without using a seed crystal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6487888A JP2712247B2 (en) | 1988-03-18 | 1988-03-18 | (II)-Method for producing bulk single crystal of group VI compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6487888A JP2712247B2 (en) | 1988-03-18 | 1988-03-18 | (II)-Method for producing bulk single crystal of group VI compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01239099A true JPH01239099A (en) | 1989-09-25 |
| JP2712247B2 JP2712247B2 (en) | 1998-02-10 |
Family
ID=13270819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6487888A Expired - Fee Related JP2712247B2 (en) | 1988-03-18 | 1988-03-18 | (II)-Method for producing bulk single crystal of group VI compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2712247B2 (en) |
-
1988
- 1988-03-18 JP JP6487888A patent/JP2712247B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2712247B2 (en) | 1998-02-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5296024B2 (en) | High pressure vessel for growing group III nitride crystals, and method for growing group III nitride crystals using high pressure vessels and group III nitride crystals | |
| KR100902525B1 (en) | Zinc oxide single crystal | |
| KR100960834B1 (en) | Hexagonal wurtzite type single crystal, process for producing the same, and hexagonal wurtzite type single crystal substrate | |
| JP4014411B2 (en) | Group III nitride crystal manufacturing method | |
| US7537659B2 (en) | Method of obtaining a CdTe or CdZnTe single crystal and the single crystal thus obtained | |
| Terashima et al. | Growth of ZnSe crystals by nonstoichiometric annealing | |
| JP2004315361A (en) | Zinc oxide single crystal | |
| JP2712247B2 (en) | (II)-Method for producing bulk single crystal of group VI compound | |
| US4299649A (en) | Vapor transport process for growing selected compound semiconductors of high purity | |
| US4439266A (en) | Vapor transport process for growing selected compound semiconductors of high purity | |
| JP3207983B2 (en) | Method for producing single crystal of group I-III-VI2 compound | |
| Pandey | A new method for the growth of Pb1− xSnxTe single crystals | |
| Hill et al. | The hydrothermal growth of beryllium oxide single crystals | |
| JP2585629B2 (en) | ZnSe single crystal preparation method | |
| Cheng et al. | Crystal Defect Investigation in PVT-Grown ZnSe Under Different Seeding Conditions and Growth Configurations Using Synchrotron X-Ray Topography | |
| JP3193440B2 (en) | Method for producing I-III-VI group 2 semiconductor single crystal | |
| JPH01264990A (en) | Method of refinning ii-vi compound semiconductor, production of ii-vi compound semiconductor single crystal and production of semiconductor light emitting element formed by using semiconductor single crystal obtained by the same method as substrate | |
| Baldochi et al. | Alexandru, HV, KDP kinetics and dislocation e $ ciency of growth 205 (1999) 215 Amano, T., see Ogasawara, M. 205 (1999) 489 Apostolaki, A., see Mavrilas, D. 205 (1999) 554 Ashida, T., see Maruyama, M. 205 (1999) 391 | |
| JPS60118700A (en) | Production of semiconductor crystal | |
| JPS5869800A (en) | Growing method for semiconductor crystal of 3[5 group element compound | |
| CN114808134A (en) | Preparation process of tellurium-zinc-cadmium single crystal wafer | |
| Triboulet | Growth of Zinc Chalcogenides | |
| JPH06263580A (en) | Method and device for producing semiconductor crystal | |
| Adam et al. | Acharya, S. and ON Srivastava, Occurrence of polytypism in SnSez 55 | |
| JPH08268791A (en) | Vertical type crystal growth method and crystal growth vessel used for the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |