JPH0231491B2 - - Google Patents
Info
- Publication number
- JPH0231491B2 JPH0231491B2 JP59113423A JP11342384A JPH0231491B2 JP H0231491 B2 JPH0231491 B2 JP H0231491B2 JP 59113423 A JP59113423 A JP 59113423A JP 11342384 A JP11342384 A JP 11342384A JP H0231491 B2 JPH0231491 B2 JP H0231491B2
- Authority
- JP
- Japan
- Prior art keywords
- discharge
- chamber
- radicals
- substrate
- growth chamber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000758 substrate Substances 0.000 claims description 19
- 239000010409 thin film Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000013076 target substance Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 238000010586 diagram Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000010894 electron beam technology Methods 0.000 description 5
- 238000000407 epitaxy Methods 0.000 description 5
- 230000005281 excited state Effects 0.000 description 5
- 238000001451 molecular beam epitaxy Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 4
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 229910003828 SiH3 Inorganic materials 0.000 description 1
- FTWRSWRBSVXQPI-UHFFFAOYSA-N alumanylidynearsane;gallanylidynearsane Chemical compound [As]#[Al].[As]#[Ga] FTWRSWRBSVXQPI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- 238000005315 distribution function Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- OLRJXMHANKMLTD-UHFFFAOYSA-N silyl Chemical compound [SiH3] OLRJXMHANKMLTD-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/24—Deposition of silicon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、VLSI回路等の半導体製造技術に関
し、等に電気的に中性で化学的に活性な分子線を
用いて低温で高品質の薄膜を精密に形成する方法
に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to semiconductor manufacturing technology such as VLSI circuits, etc., and the present invention relates to semiconductor manufacturing technology such as VLSI circuits. This invention relates to a method for precisely forming thin films.
シリコン等の半導体のエピタキシヤル層を、低
温下で高精度に形成させる方法の１つに分子線エ
ピタキシ法（通常、MBE法と呼ばれている）が
ある。第３図はその概念図であり、３１は超高真
空の成長室、３２は蒸発源、３３は電子銃、３４
は冷却用の液体窒素シユラウド、３５はシヤツ
タ、３６は薄膜を形成する基板を表わしている。
Molecular beam epitaxy (usually referred to as MBE) is one of the methods for forming epitaxial layers of semiconductors such as silicon with high precision at low temperatures. FIG. 3 is a conceptual diagram of the system, in which 31 is an ultra-high vacuum growth chamber, 32 is an evaporation source, 33 is an electron gun, and 34 is an ultra-high vacuum growth chamber.
35 is a liquid nitrogen shroud for cooling, 35 is a shutter, and 36 is a substrate on which a thin film is formed.
電子銃３３から放射された電子ビームは、蒸発
源３２の物質、たとえばシリコンSiのインゴツト
表面をたたき、そこから蒸発源物質の原子または
分子（以下分子と略記）を蒸発をさせる。蒸発し
た分子は、シヤツタ３５を通り、基板３６上にエ
ピタキシヤル層を形成させる。なお、図では省略
されているが、成長室３１内に、シリコン中へ適
当な不純物を添加する手段が設けられている。 The electron beam emitted from the electron gun 33 strikes the surface of the material of the evaporation source 32, for example, a silicon ingot, and evaporates atoms or molecules (hereinafter abbreviated as molecules) of the evaporation source material therefrom. The evaporated molecules pass through shutter 35 and form an epitaxial layer on substrate 36. Although not shown in the figure, means for adding appropriate impurities into silicon is provided in the growth chamber 31.
この従来の分子線エピタキシ法の欠点１つは、
蒸発源３２を電子ビームが照射することにより、
必然的に温度が上昇することであり、このため液
体窒素シユラウド３４を用いて冷却を行なう必要
がある。 One of the drawbacks of this conventional molecular beam epitaxy method is that
By irradiating the evaporation source 32 with an electron beam,
This inevitably results in an increase in temperature, which necessitates the use of a liquid nitrogen shroud 34 for cooling.
また他の欠点としては、シリコンのエピタキシ
ヤル成長では電子ビームの照射が蒸発源の中央部
に集中することにより、表面に凹部を生じること
である。これにより、基板３６上に入射される分
子線の均質性あるいはコリメート性が悪化して、
薄膜の厚さが場所により異なるなどの精度の低下
が生じる。またGaAsのエピタキシヤル層を形成
する場合には蒸発源はるつぼに入れたガリウムや
ひ素をそれぞれヒーター加熱しているが、成長室
内がAsガスで充満して、成長室内側や分析器等
が析出したAsにより汚染されるという問題があ
る。このため、一般には分析室と成長室とを分離
するなどの対策が講じられているが、メインテナ
ンス負担が大きいものとなる。 Another drawback is that in epitaxial growth of silicon, electron beam irradiation is concentrated at the center of the evaporation source, resulting in depressions on the surface. As a result, the homogeneity or collimation property of the molecular beam incident on the substrate 36 deteriorates,
Accuracy decreases as the thickness of the thin film varies depending on location. Furthermore, when forming an epitaxial layer of GaAs, the evaporation source heats gallium and arsenic in a crucible with a heater, but the growth chamber is filled with As gas and the inside of the growth chamber and the analyzer are heated. There is a problem of contamination with As. For this reason, countermeasures such as separating the analysis chamber and growth chamber are generally taken, but this results in a heavy maintenance burden.
従来の分子線エピタキシ法は、低温動作が困難
であり、分子線源として適用できる物質も制限さ
れ、たとえば、絶縁膜のエピタキシあるいは蒸着
ができず、また長時間の薄膜成長における均一性
などの精度にも問題がある。本発明はそのため、
従来よりもさらに多様な物質を分子線源として使
用できるようにし、しかも低温での動作を可能に
して、冷却手段を不要もしくは簡単なもので済ま
せることができるようにし、また形成される薄膜
を超高精度で制御できるようにすることである。
Conventional molecular beam epitaxy methods have difficulty operating at low temperatures and are limited in the materials that can be used as molecular beam sources.For example, they cannot epitaxy or evaporate insulating films, and they have problems with accuracy such as uniformity during long-term thin film growth. There is also a problem. Therefore, the present invention
We have made it possible to use a wider variety of materials as molecular beam sources than before, and we have also made it possible to operate at low temperatures, making cooling means unnecessary or simple, and we have made it possible to make thin films that can be formed much thinner. The goal is to enable highly accurate control.
本発明は、分子線源として従来のような電子ビ
ームやヒータなどの熱的手段によらずに、ガスを
ソースとする放電プラズマ法を用い、さらに分子
線源と成長室とを分離して、これらの間をオリフ
イスをそなえかつ差動排気された輸送管で結合す
る手段を用いるものである。
The present invention uses a discharge plasma method using a gas as a source, instead of conventional thermal means such as an electron beam or a heater, and further separates the molecular beam source from the growth chamber. A method is used to connect these parts with a transport pipe equipped with an orifice and differentially evacuated.
本発明の分子線源は、放電プラズマを用いるこ
とにより高い励起状態にある電気的に中性の原子
または分子、すなわちラジカルを多く発生するこ
とができる。このラジカルは、輸送管のオリフイ
スにより、コリメートされたラジカルビームとな
つて成長室内に放射され、基板が所定の温度に保
たれていれば、付着したラジカルが表面反応して
結晶相が析出し、薄膜を成長させる。また分子線
源の放電室は比較的高い圧力をもつが、輸送管に
おける差動排気により成長室内を超高真空に維持
することができる。
The molecular beam source of the present invention can generate many electrically neutral atoms or molecules in a highly excited state, that is, radicals, by using discharge plasma. These radicals are radiated into the growth chamber as a collimated radical beam by the orifice of the transport pipe, and if the substrate is kept at a predetermined temperature, the attached radicals will react on the surface and a crystal phase will precipitate. Grow thin films. Furthermore, although the discharge chamber of the molecular beam source has a relatively high pressure, differential pumping in the transport tube makes it possible to maintain an ultra-high vacuum inside the growth chamber.
さらに、ラジカルビームとエツチングガスとを
基板面に同時に放射し、これにレーザ等により紫
外線を局所的にすることにより、選択的なエツチ
ングと結晶成長を同時に行なうこともできる。 Furthermore, selective etching and crystal growth can be performed simultaneously by simultaneously emitting a radical beam and an etching gas onto the substrate surface, and then locally applying ultraviolet rays using a laser or the like.
〔実施例〕
以下に本発明の詳細を実施例にしたがつて説明
する。[Example] The details of the present invention will be explained below with reference to Examples.
第１図は、本発明によるラジカルビーム薄膜製
造装置の１実施例の要部構成図であり、第２図は
その全体構成図である。 FIG. 1 is a diagram showing the main part of an embodiment of the radical beam thin film manufacturing apparatus according to the present invention, and FIG. 2 is a diagram showing the entire configuration thereof.
両図において、１は放電室、２は輸送管、３は
成長室、４は放電電極、５はガス導入口、６は第
１オリフイス、７は第２オリフイス、８は基板、
９はイオン銃、１０は中速電子回析電子銃、１１
は中速電子回析スクリーン、１２はのぞき窓、１
３は４極質量分析計、１４，１５はバルブB.V.、
１６はメカニカルブースタポンプM.B.、１７は
ロータリポンプR.P.、１８は拡散ポンプD.P.、１
９はロータリポンプR.P.、２０はゲートバルブG.
V.、２１はソープシヨンポンプS.P.、２２はロー
タリポンプR.P.、２３，２４は拡散ポンプD.P.、
２５はロータリポンプR.P.を表わしている。 In both figures, 1 is a discharge chamber, 2 is a transport tube, 3 is a growth chamber, 4 is a discharge electrode, 5 is a gas inlet, 6 is a first orifice, 7 is a second orifice, 8 is a substrate,
9 is an ion gun, 10 is a medium-speed electron diffraction electron gun, 11
is a medium-speed electron diffraction screen, 12 is a viewing window, 1
3 is a quadrupole mass spectrometer, 14 and 15 are valves BV,
16 is mechanical booster pump MB, 17 is rotary pump RP, 18 is diffusion pump DP, 1
9 is rotary pump RP, 20 is gate valve G.
V., 21 is soap pump SP, 22 is rotary pump RP, 23, 24 is diffusion pump DP,
25 represents a rotary pump RP.
放電室１はガス導入口５からソースとなるガ
ス、たとえばシリコンエピタキシの場合にはモノ
シランガスSiH4が注入される。注入されたガス
は放電電極４のグロー放電により解離（クラツキ
ング）され、ラジカルが生成される。このとき同
時にイオンも生成されるが、ラカルに対する比率
は極く僅かであり、輸送管の中に設けられたイオ
ンコレクタで容易に除去することができる。グロ
ー放電の圧力領域は、およそ0.1〜1.0Torr程度で
使用され、そのため放電室内はメカニカルブース
タポンプ１６およびロータリポンプ１７により排
気されている。 A source gas, for example, monosilane gas SiH 4 in the case of silicon epitaxy, is injected into the discharge chamber 1 from a gas inlet 5. The injected gas is dissociated (cracking) by the glow discharge of the discharge electrode 4, and radicals are generated. At this time, ions are also generated, but their ratio to Racal is extremely small and can be easily removed by an ion collector installed in the transport tube. The pressure range for glow discharge is approximately 0.1 to 1.0 Torr, and therefore the interior of the discharge chamber is evacuated by a mechanical booster pump 16 and a rotary pump 17.
輸送管２は、第１オリフイス６および第２オリ
フイス７をそれぞれ有する２つのオリフイス板に
挟まれた室を形成している。これら２つのオリフ
イスは放電室１から噴射されたラジカルをコリメ
ートされたビームにして成長室３へ放射させる。
輸送管の室内は拡散ポンプ１８およびロータリポ
ンプ１９によりたとえば10-4Torr以下に排気さ
れれている。成長室３内のバツクグランドの真空
度は10-7〜10-9程度となつているので、輸送管内
は放電室１と成長室３との間の差圧を維持する機
能を果している。ゲートバルブ２０は、装置の不
使用時に成長室３を高真空状態に保持しておくた
めに使用される。 The transport pipe 2 forms a chamber sandwiched between two orifice plates each having a first orifice 6 and a second orifice 7. These two orifices convert the radicals injected from the discharge chamber 1 into a collimated beam and radiate it into the growth chamber 3.
The interior of the transport pipe is evacuated to, for example, 10 -4 Torr or less by a diffusion pump 18 and a rotary pump 19. Since the degree of background vacuum in the growth chamber 3 is approximately 10 -7 to 10 -9 , the interior of the transport tube functions to maintain the differential pressure between the discharge chamber 1 and the growth chamber 3. The gate valve 20 is used to maintain the growth chamber 3 in a high vacuum state when the apparatus is not in use.
図示の例では、第１オリフイス６の直径は１
mm、第２オリフイス７の直径は３mmである。ラジ
カルビームのフラツクス密度を上げるには、放電
室１内のプラズマの圧力を高めることと、オリフ
イスの直径を大きくすることが有効となるが、そ
のためには輸送管２内の排気能力が十分に大きい
ことが条件となる。また２つのオリフイス間の距
離をラジカルの平均自由行程よりも長くする程、
形成される薄膜の均質性は高くなる。 In the illustrated example, the diameter of the first orifice 6 is 1
mm, and the diameter of the second orifice 7 is 3 mm. In order to increase the flux density of the radical beam, it is effective to increase the pressure of the plasma in the discharge chamber 1 and to increase the diameter of the orifice, but for this purpose the exhaust capacity in the transport tube 2 is sufficiently large. This is a condition. Also, the longer the distance between the two orifices is than the mean free path of the radical, the more
The homogeneity of the formed thin film is increased.
次に、ラジカルビーム形成における反応と基板
上での薄膜形成に関与する化学反応について述べ
る。 Next, we will discuss the chemical reactions involved in radical beam formation and thin film formation on a substrate.
グロー放電中では、放電空間中での電子が電界
により加速され、得られたエネルギーが分子との
衝突の際に非弾性的に渡されることによりソース
ガスを解離させる。通常のグロー放電プラズマ中
の電子の平均的なエネルギーは、大体４〜5eVで
あるが、実際の電子分布関数上での高エネルギー
領域は10eV程度まで延びているため、大抵の分
子は解離される。たとえばシリコン薄膜の形成の
場合、モノシランガスSiH4が使用されるが、
SiH4が解離するのに必要なエネルギーは6.7eV程
度である。この解離により、SiH、SiH2などの
ラジカルと同時に原子状態のシリコン、水素、
SiH3も生成される。これらには基底状態のもの
と励起状態のものとが含まれている。 During a glow discharge, electrons in the discharge space are accelerated by an electric field, and the resulting energy is transferred inelastically upon collision with molecules, thereby dissociating the source gas. The average energy of electrons in normal glow discharge plasma is approximately 4 to 5 eV, but the high energy region on the actual electron distribution function extends to about 10 eV, so most molecules are dissociated. . For example, in the case of forming silicon thin films, monosilane gas S i H 4 is used;
The energy required for SiH 4 to dissociate is approximately 6.7 eV. This dissociation produces radicals such as SiH and SiH 2 as well as atomic silicon, hydrogen, and
SiH3 is also produced. These include ground state and excited state.
基板上では、上記のラジカルビームが照射され
ると、
SiH＋Ｈ→Si（ｓ）＋H2(g) …(1)
のように、SiHラジカルと原子状態の水素とが反
応し、シリコンが析出して水素分子が離脱する現
象が生じるものと考えられる。 When the substrate is irradiated with the above radical beam, SiH radicals react with atomic hydrogen as shown in SiH+H→Si(s)+H 2 (g) (1), and silicon is precipitated. It is thought that a phenomenon in which hydrogen molecules are released occurs.
ここで基板に到達したラジカルビーム中には、
基底状態のSiHおよびＨとともに、確率的に励起
状態のSiHおよびＨも含まれており、この励起状
態のSiHおよびＨの存在により、上記(1)式の反応
は極めて低温度で起ることになる。 In the radical beam that reached the substrate here,
Along with SiH and H in the ground state, SiH and H in the excited state are stochastically included, and due to the presence of SiH and H in the excited state, the reaction in equation (1) above occurs at an extremely low temperature. Become.
次に、ボロンナイトライド薄膜の形成の場合に
ついて述べる。このときは、ジボランとアンモニ
アの電子衝突解離反応が使用され、B2H6から
BHラジカルが生成され、そしてアンモニアから
NHラジカルが生成される。これら２つのラジカ
ルが基板上で反応することにより、ストイキオメ
トリーなボロンナイトライドが析出され、薄膜が
形成される。この反応は次のようなものと考えら
れている。 Next, the case of forming a boron nitride thin film will be described. In this case, an electron collision dissociation reaction of diborane and ammonia is used, and B 2 H 6 is
BH radicals are generated and from ammonia
NH radicals are generated. When these two radicals react on the substrate, stoichiometric boron nitride is precipitated and a thin film is formed. This reaction is thought to be as follows.
BH＋NH→BN（ｓ）＋H2(g) …(2)
次に、ガリウムひ素の場合には、たとえば
AsH3とガリウムクロライドGaCl3とを放電解離
して、GaClとAsHのラジカルを作り、
GaCl＋AsH→GaAs（ｓ）＋HCl(g) …(3)
のような表面反応を起させる。 BH+NH→BN(s)+H 2 (g) …(2) Next, in the case of gallium arsenide, for example,
AsH 3 and gallium chloride GaCl 3 are dissociated by discharge to produce radicals of GaCl and AsH, causing a surface reaction such as GaCl+AsH→GaAs(s)+HCl(g)...(3).
さらにこれにアルミニウムを加えたい場合に
は、GaCl3に対してAlCl3を置換して行けばよい。 If it is desired to further add aluminum to this, GaCl 3 may be replaced with AlCl 3 .
このように、シリコン、ボロンナイトライド、
ガリウムひ素、あるいはアルミニウムガリウムひ
素などの材料を放電解離されたラジカルビームを
用いて低温下で含成することが可能である。 In this way, silicon, boron nitride,
It is possible to contain materials such as gallium arsenide or aluminum gallium arsenide at low temperatures using a discharge dissociated radical beam.
本発明に基づくラジカルビームエピタキシ技術
の特色は、分子線が放電解離により生成されてい
ることにより、熱的制約から解放されることと、
ラジカルがもつ化学エネルギーおよび励起エネル
ギーを基板表面で解放することにより、表面の数
原子層に局所的に励起される熱振動が、吸着した
分子の表面移動を高め、エピタキシ温度を下げる
効果をもつことにある。 The features of the radical beam epitaxy technology based on the present invention are that the molecular beam is generated by discharge dissociation, so it is free from thermal constraints;
By releasing the chemical energy and excitation energy of radicals on the substrate surface, thermal vibrations locally excited in several atomic layers on the surface increase the surface movement of adsorbed molecules and have the effect of lowering the epitaxy temperature. It is in.
次に、第１図および第２図に示す装置を用いて
シリコンのエピタキシヤル成長を行なわせた１実
施例について述べる。 Next, an example will be described in which epitaxial growth of silicon was performed using the apparatus shown in FIGS. 1 and 2.
Siを含むラジカルの発生には、純モノシランガ
ス（SiH4：100％）を使用し、直流グロー放電を
行なわせた。放電室１にSiH4ガスを流量
15SCCM流し、圧力は0.3Torrに保つてグロー放
電させ、ラジカルを発生させた。発生したラジカ
ルはSi、SiH、SiH2、SiH3、Ｈであり、直径１
mmの第１オリフイス６から、予め10-8Torrまで
真空引きされた輸送管２を通り予め３×
10-9Torr以下に真空引きされた成長室３内のSi
単結晶の基板８を照射する。なお基板８は、300
〜600℃に保たれている。この時の動作状態にお
ける輸送管２および成長室３内の圧力は、それぞ
れ〜10-4Torr、〜10-6Torrであつた。基板８は、
通常の化学的な溶液を用いて洗浄した後、成長室
に入れ、真空度10-8Torrにおいて、800℃で10分
間の加熱を行ない、基板表面の清浄化を行なつた
ものである。 Pure monosilane gas (SiH 4 :100%) was used to generate radicals containing Si, and DC glow discharge was performed. Flow rate of SiH 4 gas into discharge chamber 1
15 SCCM was flowed and the pressure was maintained at 0.3 Torr to generate glow discharge and generate radicals. The generated radicals are Si, SiH, SiH 2 , SiH 3 and H, and have a diameter of 1
3 ×
Si in growth chamber 3 evacuated to below 10 -9 Torr
A single crystal substrate 8 is irradiated. Note that the board 8 is 300
It is maintained at ~600℃. The pressures in the transport tube 2 and the growth chamber 3 in the operating state at this time were ~10 -4 Torr and ~10 -6 Torr, respectively. The substrate 8 is
After cleaning with a common chemical solution, the substrate was placed in a growth chamber and heated at 800°C for 10 minutes in a vacuum of 10 -8 Torr to clean the substrate surface.
なお、作成されたSi薄膜は、ラマン散乱分光お
よび中速電子線回析によりエピタキシヤル成長し
ていることが確認されている。 Note that it has been confirmed by Raman scattering spectroscopy and medium-speed electron beam diffraction that the Si thin film thus produced is epitaxially grown.
〔発明の効果〕
以上のように本発明によれば、成長室と分子線
源とが分離されるため成長室内の温度上昇や汚染
を抑制することができ、高精度での制御が可能に
なるとともにメインテナンスも容易となる。[Effects of the Invention] As described above, according to the present invention, since the growth chamber and the molecular beam source are separated, temperature rise and contamination in the growth chamber can be suppressed, and highly accurate control becomes possible. At the same time, maintenance becomes easier.
また、放電により生成するラジカルを使用する
ため、高に励起状態のラジカルが含まれ、低温で
の薄膜成長が可能となる。さらに絶縁膜のエピタ
キシあるいはデポジシヨンのように適用可能な材
料の範囲を拡大することができる。 Furthermore, since radicals generated by discharge are used, radicals in a highly excited state are included, making it possible to grow thin films at low temperatures. Furthermore, the range of applicable materials can be expanded, such as epitaxy or deposition of insulating films.
第１図は本発明の１実施例装置の要部構成図、
第２図は全体構成図、第３図は従来の分子線エピ
タキシ法の概念図である。
図中、１は放電室、２は輸送管、３は成長室、
４は放電電極、６は第１オリフイス、７は第２オ
リフイス、８は基板を示す。
FIG. 1 is a diagram showing the main parts of a device according to an embodiment of the present invention.
FIG. 2 is an overall configuration diagram, and FIG. 3 is a conceptual diagram of a conventional molecular beam epitaxy method. In the figure, 1 is a discharge chamber, 2 is a transport tube, 3 is a growth chamber,
4 is a discharge electrode, 6 is a first orifice, 7 is a second orifice, and 8 is a substrate.
Claims (1)
よりプラズマ解離し、ラジカルを生成する放電室
と、高真空状態に保持され、内部に薄膜を形成す
べき基板をそなえている成長室と、上記放電室と
成長室とを連結し、放電室より噴射されたラジカ
ルをオリフイスによりコリメートしてビームに形
成し、成長室内に出力する輸送管とにより構成さ
れる装置において、所定のガスを上記放電室内へ
入力し、輸送管より出力されたその解離ガスのラ
ジカルビームを成長室内の基板に照射して、該基
板表面でラジカルの化学反応を生じさせることに
より目的物質を析出させることを特徴とするラジ
カルビームを用いた薄膜形成方法。1. A discharge chamber equipped with a discharge electrode to plasma-dissociate input gas by glow discharge to generate radicals, a growth chamber maintained in a high vacuum state and equipped with a substrate on which a thin film is to be formed, and the above-mentioned discharge chamber. In this device, a predetermined gas is input into the discharge chamber, and a transport tube connects the discharge chamber with the growth chamber, collimates the radicals injected from the discharge chamber into a beam using an orifice, and outputs the beam into the growth chamber. The radical beam of the dissociated gas outputted from the transport pipe is irradiated onto the substrate in the growth chamber to cause a chemical reaction of the radicals on the surface of the substrate to precipitate the target substance. Thin film formation method used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11342384A JPS60257130A (en) | 1984-06-01 | 1984-06-01 | Formation of thin film using radical beam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11342384A JPS60257130A (en) | 1984-06-01 | 1984-06-01 | Formation of thin film using radical beam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60257130A JPS60257130A (en) | 1985-12-18 |
| JPH0231491B2 true JPH0231491B2 (en) | 1990-07-13 |
Family
ID=14611859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11342384A Granted JPS60257130A (en) | 1984-06-01 | 1984-06-01 | Formation of thin film using radical beam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60257130A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6132417A (en) * | 1984-07-24 | 1986-02-15 | Mitsubishi Electric Corp | Equipment for forming thin film |
| NL1017849C2 (en) * | 2001-04-16 | 2002-10-30 | Univ Eindhoven Tech | Method and device for depositing an at least partially crystalline silicon layer on a substrate. |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5244174A (en) * | 1975-10-06 | 1977-04-06 | Hitachi Ltd | Plasma treatment device |
| JPS57159016A (en) * | 1981-03-26 | 1982-10-01 | Sumitomo Electric Ind Ltd | Manufacture of amorphous silicon film |
-
1984
- 1984-06-01 JP JP11342384A patent/JPS60257130A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5244174A (en) * | 1975-10-06 | 1977-04-06 | Hitachi Ltd | Plasma treatment device |
| JPS57159016A (en) * | 1981-03-26 | 1982-10-01 | Sumitomo Electric Ind Ltd | Manufacture of amorphous silicon film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60257130A (en) | 1985-12-18 |
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