JPH0151479B2 - - Google Patents
Info
- Publication number
- JPH0151479B2 JPH0151479B2 JP28512386A JP28512386A JPH0151479B2 JP H0151479 B2 JPH0151479 B2 JP H0151479B2 JP 28512386 A JP28512386 A JP 28512386A JP 28512386 A JP28512386 A JP 28512386A JP H0151479 B2 JPH0151479 B2 JP H0151479B2
- Authority
- JP
- Japan
- Prior art keywords
- crucible
- film forming
- forming chamber
- central
- compound 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
Links
- 239000013078 crystal Substances 0.000 claims description 46
- 239000000758 substrate Substances 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 29
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 238000003955 hot wall epitaxy Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 description 21
- 230000002093 peripheral effect Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 239000012535 impurity Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001451 molecular beam epitaxy Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004943 liquid phase epitaxy Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000000927 vapour-phase epitaxy Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000003877 atomic layer epitaxy Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【発明の詳細な説明】
本発明化合物結晶膜製造装置を以下の項目に従
つて説明する。DETAILED DESCRIPTION OF THE INVENTION The apparatus for producing a compound crystal film of the present invention will be explained according to the following items.
Ａ 産業上の利用分野
Ｂ 背景技術とその問題点
Ｃ 発明の目的
Ｄ 発明の概要
Ｅ 実施例
Ｅ−１ 実施例１
Ｅ−２ 実施例２
Ｅ−３ 実施例３
Ｅ−４ 具体例
Ｆ 発明の効果
（Ａ 産業上の利用分野）
本発明は新規な化合物結晶膜製造装置に関す
る。詳しくは、純度の高い化合物結晶膜を容易に
形成することができると共に、不純物の添加が容
易である新規な化合物結晶膜製造装置を提供しよ
うとするものである。A Industrial field of application B Background art and its problems C Objective of the invention D Summary of the invention E Example E-1 Example 1 E-2 Example 2 E-3 Example 3 E-4 Specific example F Effects (A. Industrial Application Field) The present invention relates to a novel compound crystal film manufacturing apparatus. Specifically, the present invention aims to provide a novel compound crystal film manufacturing apparatus that can easily form a compound crystal film of high purity and that can easily add impurities.
（Ｂ 背景技術とその問題点）
マイクロエレクトロニクスや光通信技術の発展
に伴い、半導体レーザー、発光ダイオード、EL
等の電光変換素子、赤外センター、太陽電池等の
光電変換素子の需要が急速に高まつて来ている。
ところが、これらの素子を製造するためには純度
の高い結晶膜が必要であるし、また、結晶膜への
不純物の添加を充分なコントロールの下に行なう
ことが必要である。(B Background technology and its problems) With the development of microelectronics and optical communication technology, semiconductor lasers, light emitting diodes, and EL
The demand for photoelectric conversion elements such as electro-optical conversion elements, infrared centers, and solar cells is rapidly increasing.
However, in order to manufacture these devices, a highly pure crystal film is required, and it is also necessary to add impurities to the crystal film under sufficient control.
しかしながら、従来の化合物結晶膜製造装置で
はこれらの要求に充分に答えられないのが現状で
ある。 However, the current situation is that conventional compound crystal film manufacturing equipment cannot sufficiently meet these demands.
例えば、MBE法（分子線エピタキシー法）に
よる製造装置は、現時点では種々の化合物結晶膜
の形成が可能な唯一の装置であるが、超高真空を
必要とし、装置が大掛りで、かつ高価となり、ま
た材料ロスが多いと共に、大型基板の処理が困難
である等の問題点がある。 For example, manufacturing equipment using the MBE method (molecular beam epitaxy) is currently the only equipment that can form various compound crystal films, but it requires ultra-high vacuum, making the equipment large-scale and expensive. In addition, there are problems such as a large amount of material loss and difficulty in processing large substrates.
また、LPE法（液相エピタキシー法）による
製造装置にあつては、高温処理が必要であるた
め、蒸気圧の高い材料には適用できない、大型基
板の処理が困難である、等の欠点を有し、更に、
CVD、ALE、スパツタリング、真空蒸着等の
VPE法（気相エピタキシー法）による製造装置
では、基板温度が高くなる、使用できる原料ガス
に制限が有る、化合物の組み合わせに制限が有
る、アモルフアスになり易い、等の欠点がある。 In addition, manufacturing equipment using the LPE method (liquid phase epitaxy) requires high temperature processing, so it has drawbacks such as not being applicable to materials with high vapor pressure, and difficulty processing large substrates. And furthermore,
CVD, ALE, sputtering, vacuum deposition, etc.
Manufacturing equipment using the VPE method (vapor phase epitaxy method) has disadvantages such as high substrate temperature, limitations on the raw material gases that can be used, limitations on the combination of compounds, and a tendency to become amorphous.
このように、従来の化合物結晶膜の製造装置に
はそれぞれ一長一短があり、種々の純度の高い化
合物結晶膜を簡単に得ることができ、また、不純
物の添加を充分なコントロールの下に行なうこと
ができ、そして、更には、その装置が簡単かつ安
価であるというようなものはない。特に、ZnSの
結晶膜の製造が可能なのはMBE法によるものの
みであり、他の方法による製造例に関してはまだ
報告がない。 As described above, each of the conventional compound crystal film production devices has its advantages and disadvantages, and it is possible to easily obtain various types of compound crystal films with high purity, and it is also possible to add impurities under sufficient control. There is nothing that can be done, and what's more, the equipment is simple and cheap. In particular, it is only possible to manufacture a ZnS crystal film by the MBE method, and there are no reports yet on examples of manufacturing by other methods.
（Ｃ 発明の目的）
そこで、本発明はHWE法（ホツトウオールエ
ピタキシー法）を用いて、前記従来の製造装置に
あつた問題点を解決して、純度の高い化合物結晶
膜を容易に形成することができると共に、不純物
の添加も容易である新基な化合物結晶膜製造装置
を提供することを目的とする。(C. Object of the invention) Therefore, the present invention uses the HWE method (hot wall epitaxy method) to solve the problems encountered with the conventional manufacturing equipment, and to easily form a compound crystal film with high purity. It is an object of the present invention to provide a novel compound crystal film manufacturing device that can easily add impurities.
（Ｄ 発明の概要）
本発明化合物結晶膜製造装置は、上記した目的
を達成するために、中心ルツボの周囲に横断面形
状で環状を為す１以上のルツボを中心ルツボと同
心に配設し、各ルツボの噴出口を膜形成室内に開
口させると共に中心ルツボの噴出口が膜形成室の
上端開口に最も近く周辺の噴出口程膜形成室の上
端開口から遠去かるようにし、更に、膜形成室の
上端開口を開閉自在に閉塞するシヤツターを設け
たホツトウオールエピタキシールツボ（HWEル
ツボ）を真空チヤンバー内に複数配置し、かつ、
化合物結晶膜形成基板を各HWEルツボの膜形成
室上端開口部に適時に移動配置せしめる手段を設
けたことを特徴とするものである。(D. Summary of the Invention) In order to achieve the above-mentioned object, the compound crystal film manufacturing apparatus of the present invention includes one or more crucibles having an annular cross-sectional shape disposed around the central crucible concentrically with the central crucible, The jet ports of each crucible are opened into the film forming chamber, and the jet port of the central crucible is closest to the upper end opening of the film forming chamber, and the peripheral jet ports are further away from the upper end opening of the film forming chamber. A plurality of hot wall epitaxy crucibles (HWE crucibles) equipped with shutters that open and close the upper end of the chamber are arranged in the vacuum chamber, and
The present invention is characterized in that a means is provided for timely moving and placing the compound crystal film forming substrate at the upper end opening of the film forming chamber of each HWE crucible.
（Ｅ 実施例）
以下に本発明化合物結晶膜製造装置の詳細を図
示した実施例に従つて説明する。(E Example) The details of the apparatus for producing a crystalline film of the compound of the present invention will be explained below according to the illustrated example.
Ｅ−１ 実施例 １
第１図及び第２図は２元材料の化合物結晶膜を
製造する化合物結晶膜製造装置の一例を示すもの
である。E-1 Example 1 FIGS. 1 and 2 show an example of a compound crystal film manufacturing apparatus for manufacturing a compound crystal film of binary materials.
１は真空チヤンバーであり、図示しないポンプ
と連結され、内部の気圧が制御されるようになつ
ている。 Reference numeral 1 denotes a vacuum chamber, which is connected to a pump (not shown) to control the internal air pressure.
２は真空チヤンバー１内に配置されたHWEル
ツボであり、膜形成室３と周辺ルツボ４と中心ル
ツボ５とが一体的に形成されて成る。 Reference numeral 2 denotes an HWE crucible disposed within the vacuum chamber 1, in which a film forming chamber 3, a peripheral crucible 4, and a central crucible 5 are integrally formed.
膜形成室３は縦断面形状で略Ｕ字状をしてお
り、その底部中央を中心ルツボ５が貫通して設け
られている。中心ルツボ５は底部が閉塞された細
長い円筒状をしており、その中央部で膜形成室３
の底部中央と結合されている。そして、中心ルツ
ボ５の上端、即ち開口端は径の細い噴出口６とさ
れており、該噴出口６と筒部との間は逆ロート状
の連続部７によつて連結されている。 The film forming chamber 3 has a substantially U-shape in longitudinal section, and a central crucible 5 is provided passing through the center of the bottom thereof. The central crucible 5 has an elongated cylindrical shape with a closed bottom, and the film forming chamber 3 is formed in the center of the crucible 5.
It is joined to the bottom center of the. The upper end of the central crucible 5, that is, the open end thereof, is formed into a narrow-diameter jet nozzle 6, and the jet nozzle 6 and the cylindrical portion are connected by a continuous portion 7 in the shape of an inverted funnel.
周辺ルツボ４は中心ルツボ５の膜形成室３内に
突出した部分と膜形成室３底部との間に形成され
る。即ち、８は周辺ルツボ形成壁であり、中心ル
ツボ５の連続部７形成位置の稍下方から中心ルツ
ボ５の壁との間に僅かの間隔を空けて下方へ向つ
て延び、膜形成室３の底部近くで、側方へ向つて
拡がつて膜形成室３の側壁と接触される、そし
て、中心ルツボ５の壁と平行に延びる垂直部９の
上端と中心ルツボ５の壁との間が噴出口１０とさ
れている。 The peripheral crucible 4 is formed between the portion of the central crucible 5 that protrudes into the film forming chamber 3 and the bottom of the film forming chamber 3. That is, reference numeral 8 denotes a peripheral crucible forming wall, which extends downward from slightly below the continuous portion 7 forming position of the central crucible 5 with a slight space between it and the wall of the central crucible 5, and extends downward from the position where the continuous portion 7 of the central crucible 5 is formed. Near the bottom, an eruption gas is formed between the upper end of the vertical part 9 which expands laterally and comes into contact with the side wall of the film forming chamber 3, and which extends parallel to the wall of the central crucible 5 and the wall of the central crucible 5. It is said to be Exit 10.
１１はウオールヒーターであり、膜形成室３の
底部（周辺ルツボ４の材料収納部となつている。）
を除いた部分の壁外面に沿つて配置されている。
１２は周辺ルツボのルツボヒーターであり、周辺
ルツボ４の材料収納部、即ち、膜形成室３の底部
を囲むように配置されている。１３は中心ルツボ
用のルツボヒーターであり、中心ルツボ５の底
部、即ち、材料収納部の外側面に沿つて配置され
ている。 Reference numeral 11 denotes a wall heater, which is located at the bottom of the film forming chamber 3 (which serves as a material storage area for the peripheral crucible 4).
It is placed along the outer surface of the wall excluding the area.
A crucible heater 12 of the peripheral crucible is arranged so as to surround the material storage section of the peripheral crucible 4, that is, the bottom of the film forming chamber 3. 13 is a crucible heater for the central crucible, and is arranged along the bottom of the central crucible 5, that is, along the outer surface of the material storage section.
１４はシヤツター兼用の基板ホルダであり、シ
ヤツター部１５と基板保持部１６とが一体に形成
されており、そして、この基板ホルダ１４は膜形
成室３の上端開口を覆うように、かつ水平方向に
スライド可能なるように配置されている。 Reference numeral 14 denotes a substrate holder that also serves as a shutter, in which a shutter portion 15 and a substrate holding portion 16 are integrally formed. It is arranged so that it can be slid.
１７は基板ヒーターであり、膜形成室３上端部
の基板ホルダ配置部に接近して配置されている。 Reference numeral 17 denotes a substrate heater, which is arranged close to the substrate holder arrangement section at the upper end of the film forming chamber 3.
１８は基板ホルダ１４の基板保持部１６に保持
される基板である。そして、基板ホルダ１４が第
２図Ａに示す状態にあるときは、HWEルツボ２
の膜形成室３の上端開口は、基板ホルダ１４のシ
ヤツター部１５によつて閉塞され、基板ホルダ１
４が第２図Ｂに示す状態にあるときは、基板１８
が膜形成室３に臨まされる。そして、基板ホルダ
１４は第２図Ａの位置と第２図Ｂの位置との間を
スライド自在に移動するようにされている。 18 is a substrate held by the substrate holding part 16 of the substrate holder 14. When the substrate holder 14 is in the state shown in FIG. 2A, the HWE crucible 2
The upper end opening of the film forming chamber 3 is closed by the shutter part 15 of the substrate holder 14, and
4 is in the state shown in FIG. 2B, the substrate 18
faces the film forming chamber 3. The substrate holder 14 is slidably moved between the position shown in FIG. 2A and the position shown in FIG. 2B.
尚、膜形成室３、中心ルツボ５及び周辺ルツボ
形成壁８は石英製のものが用いられている。 Note that the film forming chamber 3, the central crucible 5, and the peripheral crucible forming wall 8 are made of quartz.
上記の如き装置による化合物結晶膜の製造は、
各ルツボ４，５内に材料を収納し、各ヒーター１
１，１２，１３及び１７によつて膜形成室３、周
辺ルツボ４、中心ルツボ５及び基板１８を加熱
し、各ルツボ４，５内の材料を蒸発させ、各々の
噴出口１０及び６から膜形成室３内に蒸気を導入
し、基板１８上に膜を形成するものである。 Production of a compound crystal film using the above-mentioned apparatus is as follows:
The material is stored in each crucible 4, 5, and each heater 1
1, 12, 13, and 17 to heat the film forming chamber 3, peripheral crucible 4, central crucible 5, and substrate 18, evaporate the material in each crucible 4, 5, and release the film from each jet port 10 and 6. Steam is introduced into the formation chamber 3 to form a film on the substrate 18.
次に、上記装置を用いてZnS膜を形成する場合
の例を説明する。 Next, an example of forming a ZnS film using the above apparatus will be described.
周辺ルツボ４内にZnを収容し、中心ルツボ５
内にＳを収容する。 Zn is stored in the peripheral crucible 4, and the central crucible 5
Contain S inside.
そして、膜形成室３内の圧力Pd、亜鉛ルツボ
４内の圧力PZn、イオウルツボ５内の圧力PS相
互の関係を、Pd＜PZn、Pd＜PS、なる関係にな
るように、周辺ルツボ４の温度TH1及び中心ル
ツボ５の温度TH2を調整し、そして、膜形成室
３の壁温度TW、基板１８の温度TSをそれぞれ
TS＜TW、TH1＞TH2とし、これらの熱平衡下
に基板１８上にZnSの結晶膜を形成する。 Then, the temperature of the surrounding crucible 4 is adjusted so that the relationship among the pressure Pd in the film forming chamber 3, the pressure PZn in the zinc crucible 4, and the pressure PS in the sulfur crucible 5 is such that Pd<PZn, Pd<PS. Adjust the temperature TH 1 and the temperature TH 2 of the central crucible 5, and then adjust the wall temperature TW of the film forming chamber 3 and the temperature TS of the substrate 18, respectively.
TS<TW, TH 1 >TH 2 and a ZnS crystal film is formed on the substrate 18 under these thermal equilibrium conditions.
尚、イオウＳ等のように蒸気圧の高い材料を用
いる場合は、噴出口６や１０の形状に留意するこ
とが必要である。例えば、噴出口６の直径Ａを約
0.5mm、噴出口１０の幅Ｂを0.1〜0.3mm、噴出口１
０の長さＣを30mm以上とすると良い結果が得られ
る。特に、ZnSを製造する場合、Ｂの間隔が大き
く、Ｃが短かく、Ａが大きいと、蒸気圧の高いＳ
の蒸発量のコントロールが難かしく、Znルツボ
内にＳが逆拡散し、ルツボ内のZnと反応してZnS
を形成してしまい、蒸発困難となる。そこで、Ａ
を絞り、Ｂを狭くし、Ｃを長くすることで相互拡
散を防止することが可能となる。 In addition, when using a material with high vapor pressure such as sulfur S, it is necessary to pay attention to the shape of the jet ports 6 and 10. For example, the diameter A of the spout 6 is approximately
0.5mm, width B of spout 10 is 0.1 to 0.3mm, spout 1
Good results can be obtained by setting the zero length C to 30 mm or more. In particular, when manufacturing ZnS, if the distance between B is large, C is short, and A is large, S with high vapor pressure
It is difficult to control the amount of evaporation of
is formed, making it difficult to evaporate. Therefore, A
By narrowing B, making C long, it becomes possible to prevent mutual diffusion.
また、３元材料より多くの材料から成る結晶膜
を形成する場合には、真空チヤンバー内の複数の
HWEルツボを配置し、基板を各HWEルツボの
膜形成室の開口部の間に交互に位置するように移
動させれば良い。 In addition, when forming a crystalline film made of more than ternary materials, multiple
The HWE crucibles may be arranged and the substrates may be moved so as to be alternately located between the openings of the film forming chambers of the respective HWE crucibles.
Ｅ−２ 実施例 ２
第３図は本発明化合物結晶膜製造装置の第２の
実施例を示すもので、３元材料の結晶膜を形成す
るためのものである。E-2 Example 2 FIG. 3 shows a second example of the compound crystal film production apparatus of the present invention, which is for forming a crystal film of ternary materials.
これは、前記HWEルツボ２に中間ルツボ１９
が付加されたものである。中間ルツボ１９は周辺
ルツボ４と中心ルツボ５との間に壁２０と中心ル
ツボ５の外面との間の環状空間として形成され、
その噴出口２１は中心ルツボ５の噴出口６の稍下
方の位置で開口するように形成される。また、周
辺ルツボ４は中間ルツボ１９の外面と周辺ルツボ
形成壁８の内面及び膜形成室３の底部内面との間
の環状空間として形成され、その噴出口１０は中
間ルツボ１９の噴出口２１より稍下方にて開口す
るように形成される。 This is the intermediate crucible 19 in the HWE crucible 2.
is added. The intermediate crucible 19 is formed between the peripheral crucible 4 and the central crucible 5 as an annular space between the wall 20 and the outer surface of the central crucible 5;
The spout 21 is formed to open at a position slightly below the spout 6 of the central crucible 5. Further, the peripheral crucible 4 is formed as an annular space between the outer surface of the intermediate crucible 19 , the inner surface of the peripheral crucible forming wall 8 , and the inner surface of the bottom of the film forming chamber 3 , and the ejection port 10 is formed from the ejection port 21 of the intermediate crucible 19 . It is formed to open slightly below.
そして、この第３図に示したHWEルツボ２２
を用いる場合は、周辺ルツボ４の温度TH1、中
心ルツボ５の温度TH2及び中間ルツボ１９の温
度TH3が、TH1＞TH3＞TH2となる様に各材料
を各ルツボ４，５及び１９に収容することが必要
である。例えば、Zn、Ｓ、Mnから成る膜を形成
するためには、周辺ルツボ４内にMnを、中間ル
ツボ１９内にZnを、そして、中心ルツボ５内に
Ｓを収容するようにすると良い。 Then, the HWE crucible 22 shown in Fig. 3
When using , each material is placed in each crucible 4, 5 so that the temperature TH 1 of the peripheral crucible 4, the temperature TH 2 of the center crucible 5, and the temperature TH 3 of the intermediate crucible 19 satisfy TH 1 > TH 3 > TH 2 . and 19. For example, in order to form a film made of Zn, S, and Mn, it is preferable to store Mn in the peripheral crucible 4, Zn in the intermediate crucible 19, and S in the central crucible 5.
尚、このようなHWEルツボ２２が真空チヤン
バー１内に配置されることは、前記第１の実施例
におけると同様である。また、２３は中間ルツボ
１９用のルツボヒーターである。 Note that the HWE crucible 22 is arranged within the vacuum chamber 1 in the same manner as in the first embodiment. Further, 23 is a crucible heater for the intermediate crucible 19.
この場合にも、３元材料より多くの材料から成
る結晶膜を形成する場合には、真空チヤンバー内
に複数のHWEルツボを配置し、基板を各HWE
ルツボの膜形成室の開口部の間に交互に位置する
ように移動させれば良い。 In this case as well, when forming a crystalline film made of more materials than ternary materials, multiple HWE crucibles are placed in the vacuum chamber, and the substrate is placed in each HWE crucible.
They may be moved so that they are alternately located between the openings of the film forming chambers of the crucible.
Ｅ−３ 実施例 ３
第４図は本発明化合物結晶膜製造装置の第３の
実施例を示すものである。E-3 Example 3 FIG. 4 shows a third example of the compound crystal film manufacturing apparatus of the present invention.
これは、真空チヤンバー１内にHWEルツボ２
と共に蒸発ボート２４を配置したものである。 This is a HWE crucible 2 inside a vacuum chamber 1.
An evaporation boat 24 is also arranged therein.
この装置を用い、蒸発ボート２４上に添加不純
物とする材料を載置し、HWEルツボ２で結晶膜
を成長させた基板１８を蒸発ボート２４の真上ま
で移動させて、そこで、真空蒸着によつて蒸発ボ
ート２４上に載置された材料の結晶を成長させ、
これを繰り返し、かつ、基板１８の移動の時間や
結晶膜成長速度をコントロールすることによつて
化合物結晶膜の任意の場所に不純物を添加するこ
とができる。 Using this device, a material to be added as an impurity is placed on the evaporation boat 24, and the substrate 18 on which the crystal film has been grown in the HWE crucible 2 is moved to just above the evaporation boat 24, where vacuum evaporation is performed. to grow crystals of the material placed on the evaporation boat 24,
By repeating this process and controlling the time of movement of the substrate 18 and the growth rate of the crystal film, impurities can be added to any location of the compound crystal film.
例えば、HWEルツボ２で基板１８上にZnS膜
を成長させ、通常の真空蒸着でMnを（材料は蒸
発ボート２４上に載置する。）成長させることが
可能である。 For example, it is possible to grow a ZnS film on the substrate 18 in the HWE crucible 2, and to grow Mn (the material is placed on the evaporation boat 24) by normal vacuum evaporation.
Ｅ−４ 具体例
次に、本発明化合物結晶膜製造装置によるＮ型
シリコンエピタキシアルウエハー（基板）上に
ZnS膜を形成する場合の具体的手順について説明
する。E-4 Specific example Next, on an N-type silicon epitaxial wafer (substrate) using the compound crystal film manufacturing apparatus of the present invention,
A specific procedure for forming a ZnS film will be explained.
(1) 先ず、上記基板をフツ酸にてプレエツチング
を行ない、基板上の酸化膜等の不純物を取り除
き清浄面とする。(1) First, the above substrate is pre-etched with hydrofluoric acid to remove impurities such as oxide film on the substrate and make it a clean surface.
(2) 上記のプレエツチングを行なつた基板を第１
図に示す装置の基板ホルダ１４の基板保持部１
６に保持せしめる。(2) The substrate that has undergone the above pre-etching is
Substrate holder 1 of substrate holder 14 of the device shown in the figure
Hold it at 6.
(3) 純度99.999％のZnを周辺ルツボ４内に、同じ
く純度99.999％のＳを中心ルツボ５内に、それ
ぞれセツトする。(3) Set Zn with a purity of 99.999% in the peripheral crucible 4 and set S with a purity of 99.999% in the central crucible 5, respectively.
(4) 真空チヤンバー１内を10-6Torrまで真空排
気する。(4) Evacuate the inside of vacuum chamber 1 to 10 -6 Torr.
(5) 膜形成室３の上端開口を基板ホルダ１４のシ
ヤツター部１５で閉じ、周辺ルツボ４の温度
TH1が400〜450℃に、中心ルツボ５の温度
TH2が90〜100℃に、膜形成室３の壁温度TW
が450〜500℃に、基板１８の温度TSが約250℃
となるように、各ヒーター１１，１２，１３及
び１７にて加熱する。(5) Close the upper end opening of the film forming chamber 3 with the shutter part 15 of the substrate holder 14, and reduce the temperature of the surrounding crucible 4.
TH 1 is 400-450℃, temperature of central crucible 5
TH 2 is 90-100℃, wall temperature of film formation chamber 3 TW
is 450 to 500℃, and the temperature TS of the substrate 18 is approximately 250℃.
Heating is performed using each heater 11, 12, 13, and 17 so that
(6) 膜形成室３内の圧力が約10-2Torrとなつた
ところで、基板ホルダ１４をスライドさせ、基
板１８が膜形成室３の上端開口に臨むように
し、基板１８上へのZnS結晶膜の形成を開始す
る。ZnS結晶膜の堆積速度は約2μｍ／Hrであ
る。(6) When the pressure inside the film forming chamber 3 reaches approximately 10 -2 Torr, slide the substrate holder 14 so that the substrate 18 faces the upper opening of the film forming chamber 3, and deposit the ZnS crystal onto the substrate 18. Begins film formation. The deposition rate of the ZnS crystal film is approximately 2 μm/Hr.
(7) 基板１８上に形成されたZnS結晶膜が所定の
厚さとなつたら、基板ホルダ１４をスライドし
てそのシヤツター部１５で膜形成室３の上端開
口を閉じ、各ヒーター１１，，１２，１３及び
１７を止め、基板１８を冷却した後に取り出
す。(7) When the ZnS crystal film formed on the substrate 18 reaches a predetermined thickness, slide the substrate holder 14 and close the upper end opening of the film forming chamber 3 with its shutter part 15, and close each heater 11, 12, 13 and 17 are stopped, and the substrate 18 is taken out after being cooled.
以上のようにして、Ｎ型シリコンエピタキシア
ルウエハー上に形成されたZnSの結晶膜は、第５
図の高速電子反射像で見るとうり、0.15μｍと薄
い場合は単結晶であり（第５図Ａ）、また、1.5μ
ｍと厚くなつても多結晶であり（第５図Ｂ）、結
晶性の良いものであつた。 As described above, the ZnS crystal film formed on the N-type silicon epitaxial wafer is
As seen in the high-speed electron reflection image in the figure, if it is as thin as 0.15μm, it is a single crystal (Fig. 5A);
Even though it was as thick as m, it remained polycrystalline (Fig. 5B) and had good crystallinity.
（Ｆ 発明の効果）
本発明化合物結晶膜製造装置は以上に記載した
ようなもので、次のような数々の利点を有する。(F. Effects of the Invention) The compound crystal film manufacturing apparatus of the present invention is as described above, and has the following numerous advantages.
即ち、きわめて結晶性の良好な化合物結晶膜が
得られるにもかかわらず、従来の他の製造装置、
例えばMBEによる製造装置と比較して、装置が
非常に簡単である。真空蒸着装置に改造を加える
だけで製造装置が得られる、真空チヤンバー内の
真空度は10-6Torr程度で良く超高真空を必要と
しない、大型基板の処理が可能である、材料のロ
スが少ない、等数々の利点を有する。また、その
他にも、不純物をどの部分にも容易に添加するこ
とができる、多層構造の結晶膜を容易に製造する
ことができる、結晶膜生成の状態をインプロセス
で観察できる、簡単なプロセスモニター（温度コ
ントロール）でコントロールすることができ、再
現性が良好である、熱処理等の後加工を必要とし
ない、真空装置の汚れが少ない、基板温度が低く
ても良い、ルツボ内の材料の拡散によつて、異な
る材料が相互に混入するのを防止できる、等数々
の利点を有する。更には、応用範囲がきわめて広
く、種々の組み合わせ、例えば、GaAs、InSb、
ZnSe、PdSnTe、HgCdTe等々、の多元材料に
よる化合物結晶膜を作成することができる。 That is, although a compound crystal film with extremely good crystallinity can be obtained, other conventional manufacturing equipment,
For example, compared to manufacturing equipment using MBE, the equipment is very simple. A manufacturing device can be obtained by simply modifying a vacuum evaporation device, the degree of vacuum inside the vacuum chamber is only around 10 -6 Torr, and ultra-high vacuum is not required, it is possible to process large substrates, and there is no loss of material. It has many advantages such as less In addition, impurities can be easily added to any part, multilayer crystal films can be easily manufactured, and the state of crystal film formation can be observed in-process, making it a simple process monitor. (temperature control), good reproducibility, no post-processing such as heat treatment required, less contamination of vacuum equipment, low substrate temperature required, good diffusion of materials in the crucible Therefore, it has many advantages such as being able to prevent different materials from mixing with each other. Furthermore, the range of applications is extremely wide, and various combinations such as GaAs, InSb,
Compound crystal films can be created using multi-component materials such as ZnSe, PdSnTe, HgCdTe, etc.
第１図及び第２図は本発明に係る化合物結晶膜
製造装置の第１の実施例を示すもので、第１図は
全体の縦断面図、第２図は動作説明図、第３図は
本発明に係る化合物結晶膜の製造装置の第２の実
施例を示す縦断面図、第４図は本発明に係る化合
物結晶膜製造装置の第３の実施例を示す縦断面
図、第５図は本発明により製造した化合物結晶膜
の例を示す高速電子線反射像の写真である。
符号の説明、１……真空チヤンバー、２……
HWEルツボ、３……膜形成室、４……環状のル
ツボ、５……中心ルツボ、６，１０……噴出口、
１５……シヤツター、１８……基板、１９……環
状のルツボ、２１……噴出口、２２……HWEル
ツボ、２４……蒸発ボート。
1 and 2 show a first embodiment of the compound crystal film manufacturing apparatus according to the present invention, in which FIG. 1 is an overall vertical cross-sectional view, FIG. 2 is an explanatory diagram of the operation, and FIG. FIG. 4 is a vertical cross-sectional view showing a second embodiment of the compound crystal film manufacturing apparatus according to the present invention, and FIG. 5 is a vertical cross-sectional view showing the third example of the compound crystal film manufacturing apparatus according to the present invention. 1 is a photograph of a high-speed electron beam reflection image showing an example of a compound crystal film produced according to the present invention. Explanation of symbols, 1... Vacuum chamber, 2...
HWE crucible, 3... Film forming chamber, 4... Annular crucible, 5... Center crucible, 6, 10... Spout port,
15... Shutter, 18... Substrate, 19... Annular crucible, 21... Spout, 22... HWE crucible, 24... Evaporation boat.
Claims (1)
１以上のルツボを中心ルツボと同心に配置し、各
ルツボの噴出口を膜形成室内に開口させると共に
中心ルツボの噴出口が膜形成室の上端開口に最も
近く周辺の噴出口程膜形成室の上端開口から遠去
かるようにし、更に、膜形成室の上端開口を開閉
自在に閉塞するシヤツターを設けたホツトウオー
ルエピタキシールツボ（HWEルツボ）を真空チ
ヤンバー内に複数配置し、かつ、化合物結晶膜形
成基板を各HWEルツボの膜形成室上端開口部に
適時に移動配置せしめる手段を設けたことを特徴
とする化合物結晶膜製造装置。 ２ 中心ルツボの周囲に横断面形状で環状を為す
１以上のルツボを中心ルツボと同心に配置し、各
ルツボの噴出口を膜形成室内に開口させると共に
中心ルツボの噴出口が膜形成室の上端開口に最も
近く周辺の噴出口程膜形成室の上端開口から遠去
かるようにし、更に、膜形成室の上端開口を開閉
自在に閉塞するシヤツターを設け、そして、各ル
ツボ及び膜形成室の壁面を加熱する手段を設け、
膜形成室の上端開口が開放されたときに該開口上
に化合物結晶膜形成基板を配置する手段を設けた
ホツトウオールエピタキシールツボ（HWEルツ
ボ）と蒸発ボートとを真空チヤンバー内に配置
し、かつ、化合物結晶膜形成基板を適時に蒸発ボ
ート上方に移動せしめる手段を設けたことを特徴
とする化合物結晶膜製造装置。[Scope of Claims] 1. One or more crucibles having an annular cross-sectional shape are arranged around the central crucible concentrically with the central crucible, and the spout of each crucible is opened into the film forming chamber, and the spout of the central crucible is The hot wall epitaxy crucible is arranged such that the outlet closest to the upper end opening of the film forming chamber is further away from the upper end opening of the film forming chamber, and is further provided with a shutter that closes the upper end opening of the film forming chamber so as to be openable and closable. Compound crystal film production characterized by arranging a plurality of (HWE crucibles) in a vacuum chamber, and providing means for moving and arranging the compound crystal film forming substrate to the upper end opening of the film forming chamber of each HWE crucible in a timely manner. Device. 2. One or more crucibles having an annular cross-sectional shape are arranged around the central crucible concentrically with the central crucible, and the jet ports of each crucible are opened into the film forming chamber, and the jet port of the central crucible is located at the upper end of the film forming chamber. The outlet closest to the opening is further away from the upper end opening of the film forming chamber, and a shutter is provided to freely open and close the upper end opening of the film forming chamber, and the walls of each crucible and the film forming chamber are provide means for heating the
A hot wall epitaxy crucible (HWE crucible) provided with a means for arranging a compound crystal film forming substrate over the opening when the upper end opening of the film forming chamber is opened, and an evaporation boat are arranged in the vacuum chamber, and 1. A compound crystal film manufacturing apparatus, comprising a means for moving a compound crystal film forming substrate above an evaporation boat in a timely manner.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28512386A JPS62143894A (en) | 1986-11-29 | 1986-11-29 | Apparatus for production of compound crystal film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28512386A JPS62143894A (en) | 1986-11-29 | 1986-11-29 | Apparatus for production of compound crystal film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58030094A Division JPS59156996A (en) | 1983-02-23 | 1983-02-23 | Method and device for manufacturing crystalline film of compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62143894A JPS62143894A (en) | 1987-06-27 |
| JPH0151479B2 true JPH0151479B2 (en) | 1989-11-02 |
Family
ID=17687413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28512386A Granted JPS62143894A (en) | 1986-11-29 | 1986-11-29 | Apparatus for production of compound crystal film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62143894A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0752716B2 (en) * | 1990-06-05 | 1995-06-05 | 松下電器産業株式会社 | Pyrolysis cell |
-
1986
- 1986-11-29 JP JP28512386A patent/JPS62143894A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62143894A (en) | 1987-06-27 |
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