JPH01232715A - Manufacture of semiconductor structure - Google Patents
Manufacture of semiconductor structureInfo
- Publication number
- JPH01232715A JPH01232715A JP63058263A JP5826388A JPH01232715A JP H01232715 A JPH01232715 A JP H01232715A JP 63058263 A JP63058263 A JP 63058263A JP 5826388 A JP5826388 A JP 5826388A JP H01232715 A JPH01232715 A JP H01232715A
- Authority
- JP
- Japan
- Prior art keywords
- crystal
- electron beam
- grow
- caf2
- atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 34
- 238000010894 electron beam technology Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000001093 holography Methods 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000000470 constituent Substances 0.000 claims abstract description 3
- 239000010409 thin film Substances 0.000 claims abstract 4
- 238000000151 deposition Methods 0.000 claims 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 abstract description 9
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract description 8
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract description 7
- 238000010884 ion-beam technique Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 125000004429 atom Chemical group 0.000 description 8
- 238000001451 molecular beam epitaxy Methods 0.000 description 8
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 230000033764 rhythmic process Effects 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
Landscapes
- Drying Of Semiconductors (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
- Recrystallisation Techniques (AREA)
- Semiconductor Lasers (AREA)
- Light Receiving Elements (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は量子効果の顕著な半導体構造体の製造に係り、
特に、超高速の受光素子あるいは半導体レーザに好適な
量子細線、量子箱構造の半導体構造体の製造方法に関す
る。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to the production of semiconductor structures with remarkable quantum effects,
In particular, the present invention relates to a method of manufacturing a semiconductor structure having a quantum wire or quantum box structure suitable for ultra-high-speed light receiving elements or semiconductor lasers.
量子細線を作製する方法については、これまでに、結晶
の異方性エツチングを利用した方法についてアプライド
・フィジックス・レター 第４１巻６３５頁（１９８２
年） （Ａｐｐｌ、 Ｐｈｙｓ、 Ｌｅｔｔ、 ４１１
９８２ｐ、６３５）に、電子ビームリングラフィ法と超
格子の不純物誘起混晶化とを用いた方法について上記誌
第４９巻１２７５頁（１９８６年） （Ａｐｐｌ、Ｐｈ
ｙｓ、 Ｌｅｔｔ。Regarding the method for producing quantum wires, we have so far described a method using anisotropic etching of crystals in Applied Physics Letters, Vol. 41, p. 635 (1982).
) (Appl, Phys, Lett, 411
982p, 635), the above-mentioned journal Vol. 49, p. 1275 (1986) (Appl, Ph.
ys, Lett.
４９１９８６ ｐ、１２７５）に記載がある。491986 p. 1275).
しかしながら、前記従来技術の方法は、細線の幅寸法お
よび均一性の点で不十分であり、量子サイズ効果が顕著
にあられれる２００Å以下の量子井戸構造を得ることは
できなかった。すなわち、これらの方法において、量子
細線のパターンは電子ビームを走査させることによって
形成しているが、その寸法の均一性および線量は量子細
線の幅寸法を決定する重要な因子であり、量子準位と密
接に関連しているにもかかわらず、走査電子線の安定性
の点から、優れた均一性を得ることが難しかった。However, the method of the prior art is insufficient in terms of the width and uniformity of the thin wire, and it has not been possible to obtain a quantum well structure of 200 Å or less in which the quantum size effect is noticeable. In other words, in these methods, the quantum wire pattern is formed by scanning an electron beam, but the uniformity of the dimensions and the dose are important factors that determine the width of the quantum wire, and the quantum level However, it has been difficult to obtain excellent uniformity due to the stability of the scanning electron beam.
また、上記の問題点を解決する方法として、電子線ホロ
グラフィを用いることによって均一な周期と幅とを有す
る量子細線を作製する方法が特開昭第６２−１４０４８
５号に開示されているが、この場合、電子線ホログラフ
ィで得られた電子線レジストの微細パターンを化合物半
導体に転写する過程で。In addition, as a method to solve the above problems, a method for producing quantum wires with uniform period and width by using electron beam holography was published in Japanese Patent Application Laid-Open No. 62-14048.
No. 5, in this case, in the process of transferring a fine pattern of electron beam resist obtained by electron beam holography onto a compound semiconductor.
結晶を真空の外へ取り出したり、現像処理によりレジス
トを除去して結晶を再成長させる手段を用いるため、最
も重要な量子細線部が不純物によって汚染される可能性
があった。また、電子線レジストの微細パターンを基板
結晶に転写する方法として微細パターンによって形成さ
れたマスクを介してＧａイオンを打ち込み、これをアニ
ールする際に生ずる超格子の混晶化の現象を利用してい
るため、微細パターンがそのまま微細へテロ構造となら
ず、ぼけを生ずる可能性があった。Since the method involves taking the crystal out of a vacuum or removing the resist through development treatment to re-grow the crystal, there is a possibility that the most important quantum wire region may be contaminated with impurities. In addition, as a method of transferring a fine pattern of electron beam resist to a substrate crystal, Ga ions are implanted through a mask formed by the fine pattern, and the phenomenon of mixed crystallization of the superlattice that occurs when annealing is used. Therefore, there is a possibility that the fine pattern does not become a fine heterostructure as it is, resulting in blurring.
以上述べたような状況から、従来技術においては、 １
００Å以下の量子細線あるいは量子箱を得ることが極め
て難しい状態にあった。From the above-mentioned situation, in the conventional technology, 1.
It has been extremely difficult to obtain quantum wires or quantum boxes with a thickness of 00 Å or less.
本発明の目的は、上記従来技術の有していた課題を解消
し、超高速の受光素子あるいは半導体レーザに好適な、
微細な量子細線構造の半導体構造体を、容易に、かつ、
極めて高い均一性をもって製造する方法を提供すること
にある。An object of the present invention is to solve the problems of the above-mentioned conventional techniques, and to provide a method suitable for ultra-high-speed light receiving elements or semiconductor lasers.
Easily and easily create semiconductor structures with fine quantum wire structures.
The object of the present invention is to provide a manufacturing method with extremely high uniformity.
上記目的は、極めて均質性の優れた微細パターンを与え
る電子線ホログラフィによる電子の定在波のパターンを
、そのまま、基板結晶上のへテロ構造に転写し、そのパ
ターンを用いて半導体結晶を選択的に成長させること、
特に、ペテロ構造へのパターン転写の方法として、電子
線を照射した場所だけが化学的に活性化し、選択的な半
導体結晶の成長を生じ得る方法をとること、によって、
達成することができる。The above purpose is to directly transfer the standing wave pattern of electrons produced by electron beam holography, which produces a fine pattern with extremely high homogeneity, onto a heterostructure on a substrate crystal, and use that pattern to selectively form a semiconductor crystal. to grow into
In particular, as a method of pattern transfer to the Peter structure, only the areas irradiated with the electron beam are chemically activated, resulting in selective semiconductor crystal growth.
can be achieved.
具体例を挙げて説明すれば、基板半導体としてＧａＡｓ
を用い、該基板上にＣａＦ、層を設け、該層上に電子線
ホログラフィを照射してパターンを作成した後、Ｇａお
よびＡｓの分子線を照射してパターン状にＧａＡｓの結
晶成長を行わせることによる。To explain with a specific example, GaAs is used as a substrate semiconductor.
A CaF layer is provided on the substrate using a method, a pattern is created by irradiating the layer with electron beam holography, and then Ga and As molecular beams are irradiated to grow GaAs crystals in a pattern. It depends.
ＧａＡｓ基板、結晶上に、バッファ層（例えばＡ（ｌＧ
ａＡｓ）を介して、ＣａＦ２を数原子層蒸着すると、格
子定数の差が小さいために、ＣａＦ２は単結晶の層を形
成する。この表面に電子線ホログラフィを照射すると、
電子線ホログラフィの格子状パターンの電子密度の高い
領域に対応するＣａＦ、のふっ素（Ｆ）ｉ子が除去され
、その部分には活性化されたＣａ原子が残存する。得ら
れた表面にＧａおよびＡｓの分子線を照射すると、まず
、上記活性化ＣａとＡｓとが結合し、続いて、その−ヒ
にＧａＡｓ結晶が成長する結果、ＧａＡｓの量子細線が
電子線ホログラフィのパターン状に形成されることにな
る。A buffer layer (for example, A(lG
When several atomic layers of CaF2 are deposited through aAs), CaF2 forms a single crystal layer because the difference in lattice constant is small. When this surface is irradiated with electron beam holography,
Fluorine (F) i atoms of CaF corresponding to regions with high electron density in the lattice pattern of electron beam holography are removed, and activated Ca atoms remain in those regions. When the obtained surface is irradiated with molecular beams of Ga and As, the activated Ca and As bond together, and then GaAs crystals grow on the surface. It will be formed in a pattern.
以下１本発明の製造方法について実施例によって具体的
に説明する。Hereinafter, the manufacturing method of the present invention will be specifically explained with reference to Examples.
実施例 １
第７図は、分子線エピタキシ装置に超高真空の搬送路を
介して接続される、本実施例に用いた電子線ホログラフ
ィ照射装置の概略構成を示した図で、非干渉性の良い、
電子ビームを発生する電子線源１、レンズ系２および３
、パイプリズム４からなることを示す。ここで、加速電
圧５０ｋ Ｖをもって電子線源１から取り出された電子
ビームはレンズ系２および３によってコリメートされ、
さらに。Example 1 Figure 7 is a diagram showing the schematic configuration of the electron beam holography irradiation device used in this example, which is connected to the molecular beam epitaxy device via an ultra-high vacuum conveyance path. good,
An electron beam source 1 that generates an electron beam, lens systems 2 and 3
, shows that it consists of 4 pipe rhythms. Here, the electron beam taken out from the electron beam source 1 with an accelerating voltage of 50 kV is collimated by lens systems 2 and 3,
moreover.
パイプリズム４によって２分割され、２分割された電子
ビーム５は、交差角を調整することによって、試料６上
に定在波（電子線ホログラム）７を生ずる。本実施例に
おいては、定在波７の周期が１００人となるようにビー
ム交差角を調整した。The electron beam 5 is divided into two by the pipe prism 4, and by adjusting the intersection angle, a standing wave (electron beam hologram) 7 is generated on the sample 6. In this example, the beam intersection angle was adjusted so that the period of the standing wave 7 was 100 people.
まず、第１図に示すように１分子線エピタキシ装置にお
いて、Ｇ ａ Ａ ｓ結晶基板８上にバッファ層Ａｎ、
、３Ｇａ、、７Ａｓ９を１ｕｒａの厚さに分子線エピタ
キシ成長させた後、ＣａＦ２を数原子層蒸着し。First, as shown in FIG. 1, in a single molecular beam epitaxy apparatus, a buffer layer An,
, 3Ga, , 7As9 were grown by molecular beam epitaxy to a thickness of 1 ura, and several atomic layers of CaF2 were then deposited.
ＣａＦ２層１０を形成した。次いで、この試料を搬送路
を通して電子線ホログラフィ装置に移し、１ｘ１０−Ｔ
ｏｒｒ以上の高真空中で電子線ホログラフィ照射を行
った。ここで、定在波７の電子密度の高い領域のＣａＦ
２からＦ原子が離脱し、活性なＣａ原子が表面にあられ
れた領域１１が形成される。A CaF2 layer 10 was formed. Next, this sample was transferred to an electron beam holography device through a transport path, and a 1x10-T
Electron beam holography irradiation was performed in a high vacuum of orr or higher. Here, CaF in the region of high electron density of the standing wave 7
F atoms are separated from 2, and a region 11 where active Ca atoms are present on the surface is formed.
さらに、試料を、再び１分子線エピタキシ８ＡＩｉ！に
戻し、ＧａおよびＡｓの分子線の照射を行った。ここで
、第２図に示したように、活性化Ｃａ原子が存在する領
域１１のみにＧａＡｓ結晶が成長し、幅１００人、長さ
２Ｉ！ｍの量子細線１２が得られる。次いで、残存する
ＣａＦ、をイオンビームの照射により除去した後、分子
線エピタキシにより
４党。、ＪＧａｏ、、Ａｓ層１３を成長させて量子細線
１２を埋め込み、第３図に示したような完成品を得た。Furthermore, the sample was again subjected to single molecular beam epitaxy 8AIi! The temperature was returned to 100.degree., and irradiation with Ga and As molecular beams was performed. Here, as shown in FIG. 2, a GaAs crystal grows only in the region 11 where activated Ca atoms exist, and has a width of 100 mm and a length of 2 I! m quantum wires 12 are obtained. Next, remaining CaF was removed by ion beam irradiation, and then subjected to molecular beam epitaxy. , JGao, , an As layer 13 was grown and a quantum wire 12 was embedded therein to obtain a finished product as shown in FIG.
得られた量子細線について、ホトルミネセンス法を用い
て、７７にで評価した結果、６８０ｎ＋ａの発光が観測
された。この値は、ＧａＡｓのバルク結晶あるいは結晶
の厚さ方向にのみ量子井戸を形成した試料に比べ短波長
であり、このことから、結晶の成長方向に対して直角方
向に、１００人の幅で量子閉じ込めの生じていることが
知られた。The obtained quantum wire was evaluated in 77 using a photoluminescence method, and as a result, light emission of 680n+a was observed. This value is shorter than that of a GaAs bulk crystal or a sample in which quantum wells are formed only in the thickness direction of the crystal. It was known that confinement had occurred.
実施例 ２
実施例１の場合と同様にして、まず１分子線エピタキシ
装置において、ＩｎＰ基板上にＩｎＡｌｌＡｓを１−の
厚さに成長させ、さらにＢａＦ、を数原子層形成した後
、試料を電子線ホログラフィ装置に移し、ｆｔ！子ホロ
グラフィの照射を行って定在波の電子密度の高い領域の
ＢａＦ、のＦｙＸ子の脱離を行い、周期１５０人の格子
状のパターン１４を作成した（第４図）０次いで、同装
置中で、試料を９０°回転した状態で、再度、電子線ホ
ログラフィ照射を行った。その状態を第５図に示す。次
いで、試料を、再度、分子線エピタキシ装置に戻し、分
子線エピタキシによりＩｎＧａＡｓ結晶の成長を行った
。Example 2 In the same manner as in Example 1, InAllAs was first grown to a thickness of 1- on an InP substrate using a single molecular beam epitaxy apparatus, and several atomic layers of BaF were then formed, and then the sample was exposed to electrons. Transfer to a line holography device, ft! A lattice-like pattern 14 with a period of 150 people was created by irradiating the electron holography to desorb FyX atoms of BaF in the region of high electron density of the standing wave (Fig. 4). Inside, the sample was rotated 90° and irradiated with electron beam holography again. The state is shown in FIG. Next, the sample was returned to the molecular beam epitaxy apparatus again, and an InGaAs crystal was grown by molecular beam epitaxy.
このとき、電子線照射が重複して行われた領域１６は、
Ｂａ原子が脱離しているために、ＩｎＧａＡｓ結晶が成
長せず、また、電子線照射が行われなかった領域１７も
またＩｎＧａＡｓ結晶が成長しない１９ため、第６図に
みられるように、市松模様状に分布したＩｎＧａＡｓ結
晶の量子箱１８が得られた。At this time, the area 16 where the electron beam irradiation was performed in duplicate is
Because the Ba atoms are detached, InGaAs crystals do not grow, and InGaAs crystals also do not grow in the region 17 where electron beam irradiation was not performed19, resulting in a checkered pattern as shown in FIG. A quantum box 18 of InGaAs crystal distributed in a shape was obtained.
〔発明の効果〕
以上述べてきたように、量子効果の顕著な半導体構造体
の製造において、本発明の方法、すなわち、半導体結晶
基板表面にイオン結晶を被着させ、電子線ホログラフィ
によって該イオン結晶の構成原子をパターン状に離脱さ
せ、該原子離脱の領域のみに選択的に半導体結晶成長を
行わせる方法。[Effects of the Invention] As described above, in the production of semiconductor structures with remarkable quantum effects, the method of the present invention is used: ionic crystals are deposited on the surface of a semiconductor crystal substrate, and the ionic crystals are formed by electron beam holography. A method in which the constituent atoms of are separated in a pattern, and semiconductor crystal growth is selectively performed only in the region where the atoms are separated.
をとることによって、従来技術の有していた課題を解消
し、超高速の受光素子あるいは半導体レーザに好適な量
子細線構造あるいは量子箱を容易に、かつ、極めて高い
均一性をもって製造することができた。By adopting this method, the problems of conventional technology can be solved, and quantum wire structures or quantum boxes suitable for ultra-high-speed photodetectors or semiconductor lasers can be manufactured easily and with extremely high uniformity. Ta.
第１〜３図は本発明の方法により量子細線を作成する工
程を示した試料概略断面図、第４〜６図は本発明の方法
により量子箱を作成する工程を示した試料概略平面図、
第７図は電子線ホログラフィ装置の構成を示す概要図で
ある。
１・・・電子線源 ２，３・・・レンズ系４・
・・パイプリズム
５・・・２分割された電子ビーム
６・・・試料 ７・・・定在波８・・・結
晶基板（ＧａＡｓ）
９・・・バッファ層（ＡＩＬＩＩ １ａ ａｏ、７ Ａ
ｓ）１０・・・ＣａＦ、層 １１・・・Ｆ原子
離脱部１２−＝量子細線（ＧａＡｓ）
１３ ・・・埋め込み層（Ａ１１６１Ｇ ａｎ 、 ７
Ａ ９）１４、１５・・・ＦＭ子子離領領
域１６・・Ｃａ離脱領域
１７・・・電子線照射が行われなかった領域１８・・・
量子箱
１９・・・結晶成長の行われない領域
代理人弁理士 中 村 純之助
昂ω 〜−■の
門へ＋Ｃｒ）（１）1 to 3 are schematic cross-sectional views of a sample showing the steps of creating a quantum wire by the method of the present invention, and FIGS. 4 to 6 are schematic plan views of the sample showing the steps of creating a quantum box by the method of the present invention,
FIG. 7 is a schematic diagram showing the configuration of an electron beam holography device. 1... Electron beam source 2, 3... Lens system 4.
... Pipe rhythm 5 ... Electron beam divided into two 6 ... Sample 7 ... Standing wave 8 ... Crystal substrate (GaAs) 9 ... Buffer layer (AILII 1a ao, 7 A
s) 10...CaF, layer 11...F atom separation part 12-=quantum wire (GaAs) 13...buried layer (A1161G an, 7
A 9) 14, 15... FM separation area 16... Ca separation area 17... Area 18 where electron beam irradiation was not performed...
Quantum Box 19... Area where crystal growth does not occur Junnosuke Nakamura, Attorney-at-Law Patent Attorney Toward the Gate of ~-■+Cr) (1)
Claims (1)
、次いで、該イオン結晶の構成原子を電子線ホログラフ
ィ法によりパターン的に離脱させた後、さらに、該表面
に、分子線照射等により、結晶成長を行わせることによ
って、上記原子離脱の生じた領域のみに、選択的に半導
体結晶の成長を行わせることを特徴とする半導体構造体
の製造方法。 ２、上記イオン結晶薄膜がＣａＦ＿２あるいはＢａＦ＿
２からなる薄膜であることを特徴とする特許請求の範囲
第１項記載の半導体構造体の製造方法。[Claims] 1. After depositing an ionic crystal thin film on the surface of a semiconductor crystal substrate, and then removing the constituent atoms of the ionic crystal in a pattern by electron beam holography, further depositing on the surface, A method for manufacturing a semiconductor structure, characterized in that semiconductor crystal growth is selectively performed only in the region where the atom detachment has occurred by performing crystal growth using molecular beam irradiation or the like. 2. The above ionic crystal thin film is CaF_2 or BaF_
2. The method of manufacturing a semiconductor structure according to claim 1, wherein the thin film is made of 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63058263A JPH01232715A (en) | 1988-03-14 | 1988-03-14 | Manufacture of semiconductor structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63058263A JPH01232715A (en) | 1988-03-14 | 1988-03-14 | Manufacture of semiconductor structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01232715A true JPH01232715A (en) | 1989-09-18 |
Family
ID=13079276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63058263A Pending JPH01232715A (en) | 1988-03-14 | 1988-03-14 | Manufacture of semiconductor structure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01232715A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5466548A (en) * | 1993-07-29 | 1995-11-14 | Nec Corporation | Method for producing nanometer order dot pattern by electron holography and drawing apparatus for the same |
-
1988
- 1988-03-14 JP JP63058263A patent/JPH01232715A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5466548A (en) * | 1993-07-29 | 1995-11-14 | Nec Corporation | Method for producing nanometer order dot pattern by electron holography and drawing apparatus for the same |
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