JPS63232338A - Chemical vapor phase epitaxy method - Google Patents
Chemical vapor phase epitaxy methodInfo
- Publication number
- JPS63232338A JPS63232338A JP6657687A JP6657687A JPS63232338A JP S63232338 A JPS63232338 A JP S63232338A JP 6657687 A JP6657687 A JP 6657687A JP 6657687 A JP6657687 A JP 6657687A JP S63232338 A JPS63232338 A JP S63232338A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- electron beam
- chemical vapor
- reactive gas
- vapor deposition
- 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
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000126 substance Substances 0.000 title 1
- 238000000927 vapour-phase epitaxy Methods 0.000 title 1
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 238000010894 electron beam technology Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 31
- 238000005229 chemical vapour deposition Methods 0.000 claims description 19
- 239000012495 reaction gas Substances 0.000 claims description 7
- 230000005686 electrostatic field Effects 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000010408 film Substances 0.000 abstract description 21
- 239000010409 thin film Substances 0.000 abstract description 7
- 230000003068 static effect Effects 0.000 abstract 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 6
- 230000005684 electric field Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- ZFXYFBGIUFBOJW-UHFFFAOYSA-N theophylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1NC=N2 ZFXYFBGIUFBOJW-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は化学気相成長法に関し、特に４００℃以下の低
温で反応ガスを分解し基板上に半導体デバイスに用いら
れる薄膜膜形成する化学気相成長法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a chemical vapor deposition method, in particular a chemical vapor deposition method that decomposes a reactive gas at a low temperature of 400°C or less to form a thin film on a substrate for use in semiconductor devices. It is related to phase growth method.
半導体デバイスに用いられる薄＠を低温で形成するため
の従来の技術としては、プラズマ化学気相成長法（例え
ば、管野卓雄編著二半導体プラズマプロセス技術、産業
図書、１９８０年）あるいは光化学気相成長法（例えば
、Ｋ、 Ｈａｍａｎｏ ｅｔ 。Conventional techniques for forming thin films used in semiconductor devices at low temperatures include plasma chemical vapor deposition (for example, 2 Semiconductor Plasma Process Technology, edited by Takuo Kanno, Sangyo Tosho, 1980) and photochemical vapor deposition. (For example, K. Hamano et.
ａｌ 、Ｊｐｎ、 Ｊ、 Ａｐｐｌ 、 Ｐｈｙ、 ２
３ （１９８４） １２０９−１２１５ ）がある。al, Jpn, J, Appl, Phy, 2
3 (1984) 1209-1215).
プラズマ化学気相成長法は、ガス導入部、真空酸すべき
基板をのせた電極と高周波電極とを対向させて配置し、
両電極間に高周波電圧を印加することによｐ反応ガスを
放電し分解させることによリーー −
−基板上
に成膜する。In the plasma chemical vapor deposition method, a gas inlet, an electrode carrying the substrate to be vacuum-oxidized, and a high-frequency electrode are placed facing each other.
By applying a high frequency voltage between both electrodes, the p-reactive gas is discharged and decomposed.
- Depositing a film on a substrate.
また、光化学気相成長法はガス導入部、真空排気系、お
よび光源部を備えた反応炉を用いて行なわれる。通常、
光源部からの紫外光を光照射窓を通し反応炉内の反応ガ
スに照射し、このガスを光分解することによって中性ラ
ジカルを生成することにより反応炉内に設置された基板
上に成膜を行う。Further, the photochemical vapor deposition method is performed using a reactor equipped with a gas introduction section, a vacuum exhaust system, and a light source section. usually,
Ultraviolet light from the light source is irradiated through the light irradiation window onto the reactant gas inside the reactor, and this gas is photolyzed to generate neutral radicals, thereby forming a film on the substrate installed inside the reactor. I do.
上述した従来のプラズマ化学気相成長法では、電極間に
ダロー放電が生じた状態で、電極板上に置かｎた基板上
に薄膜を成長するため、電極近傍に形成された７°ラズ
マ・シースによって加速されたイオンおよび電子が、基
板および基板上に形成された薄膜に損傷を与えるため形
成される薄膜の物理的・電気的特性が劣化するという欠
点がある。In the conventional plasma chemical vapor deposition method described above, in order to grow a thin film on a substrate placed on an electrode plate with a Darrow discharge occurring between the electrodes, a 7° lasma sheath formed near the electrodes is used. The accelerated ions and electrons damage the substrate and the thin film formed on the substrate, resulting in deterioration of the physical and electrical properties of the formed thin film.
また、上述した従来の光化学気相成長法は、プラズマ化
学気相成長法にみられる基板損傷はほとんど無いが、光
励起される反応ガス分子数が少ないため膜の成長速度が
小さいという欠点がある。Furthermore, although the above-described conventional photochemical vapor deposition method causes almost no damage to the substrate as seen in plasma chemical vapor deposition, it has the disadvantage that the film growth rate is low because the number of reactive gas molecules that are photoexcited is small.
本発明の化学気相成長法は、反応ガスを原料として使用
し、パルス電子線を照射した状態で、基板上に膜形成全
行なっている。In the chemical vapor deposition method of the present invention, a reaction gas is used as a raw material, and a film is entirely formed on a substrate under irradiation with a pulsed electron beam.
このパルス電子縁は、反応ガスあるいは反応カスと基板
に照射される。This pulsed electron beam irradiates the reaction gas or reaction residue and the substrate.
このようにパルス電子＃１−反応ガスあるいは反応ガス
と基板とに照射した状態でさらに基板に紫外光を照射す
ることもできる。It is also possible to further irradiate the substrate with ultraviolet light while the pulsed electron #1-reactant gas or the reaction gas and the substrate are irradiated in this manner.
また、基板に向かう静電場が形成された状態で、パルス
電子線を照射することもできる。Further, the pulsed electron beam can also be irradiated with an electrostatic field directed toward the substrate.
本発明による手法によれば、反応ガス中に０．１〜ｌＯ
ＭｅＶの高エネルギー電子紛ヲパルス的に入射すること
Ｋよジ、数’ｌ’ ｏ ｒ ｒ〜数百Ｔｏｒｒ圧力下で
高密度の電離気体をつくることができる。その結果、成
膜反応に必要な分子ラジカルを効率よく生成で、きるこ
とから高速度の膜成長を行うことができる。しかも、通
常のプラズマ化学気相成長法においては電極板上に基板
を設置するため電極板近傍の高電場のプラズマ・シース
で加速された高エネルギー荷電粒子の損傷を受けるが、
本発明の化学気相成長法では１ＪＬ離気体と基板間に高
電場をかけずに反応ガスを電離するため荷電粒子による
基板損傷を全く受けず電気的特性の優れた膜を形成する
ことができる。According to the method according to the invention, 0.1 to 1O
By injecting MeV high-energy electron particles in a pulsed manner, it is possible to create a high-density ionized gas under a pressure of several liters to several hundred Torr. As a result, the molecular radicals necessary for the film-forming reaction can be efficiently generated, allowing high-speed film growth. Moreover, in the normal plasma chemical vapor deposition method, the substrate is placed on the electrode plate, so it is damaged by high-energy charged particles accelerated by the high electric field plasma sheath near the electrode plate.
In the chemical vapor deposition method of the present invention, the reactive gas is ionized without applying a high electric field between the 1JL separating gas and the substrate, so it is possible to form a film with excellent electrical properties without causing any damage to the substrate due to charged particles. .
同時に１基板表面に紫外光を照射すること、あるいは静
電場を用いて電離気体中のイオンに一定ションを促進す
るため、よシ緻密な腺を形成することができる。At the same time, a very dense gland can be formed by irradiating the surface of one substrate with ultraviolet light or by using an electrostatic field to promote a certain amount of ions in the ionized gas.
次に、本発明について図面を参照して説明する。 Next, the present invention will be explained with reference to the drawings.
第１図は本発明の第１の実施例において、化学気相成長
を行うための装置の縦断面図である。膜成長を行う反応
炉１０１．パルス電子線を発生する電子線加速器１０２
．低圧水銀灯１０３．合成石英窓１０４．ヒータ１０５
．ガス導入口１０６゜カス排気口１０７．基板１０８．
原料ガスボンベ１０９．１１０を備えている。FIG. 1 is a longitudinal sectional view of an apparatus for performing chemical vapor deposition in a first embodiment of the present invention. Reactor 101 for film growth. Electron beam accelerator 102 that generates a pulsed electron beam
．． Low pressure mercury lamp 103. Synthetic quartz window 104. Heater 105
．． Gas inlet port 106° Waste exhaust port 107. Substrate 108.
It is equipped with raw material gas cylinders 109 and 110.
本実施例により窒化珪素膜全形成する手順について述べ
る。基板１０８ｔヒータ１０５上に設置し、ヒータ１０
５によシ３００℃に加熱した後、シラ７ｋ １０〜５０
５ｅｃｆｎ 、アンモニアを１００〜３ Ｑ Ｑ ＳＣ
Ｃｍガス導入口１０６よシ流入し、ガス排気口１０７か
らの排気速度を調節することによって、反応炉１０１内
のガス圧が一数Ｔｏｒｒの定常流を形成する。The procedure for forming the entire silicon nitride film according to this embodiment will be described. The heater 10 is installed on the substrate 108t and the heater 105.
5 After heating to 300℃, Shira 7k 10-50
5ecfn, ammonia from 100 to 3 Q Q SC
By adjusting the speed of Cm gas flowing in through the gas inlet 106 and exhausting from the gas exhaust port 107, a steady flow with a gas pressure of several Torr in the reactor 101 is formed.
次に、電子線加速器１０２により、０．６ Ｍ ｅ Ｖ
。Next, by the electron beam accelerator 102, 0.6 M e V
.
ＩＱＫＡ、パルス幅５ｎｓのパルス電子ｉを照射し、反
応炉１０１内の反応ガスを励起すると同時に、低圧水銀
灯１０３を点灯し基板１０８に垂直に紫外光を照射し基
板１０８表面を励起し、基板１０８上に窒化硅素膜を成
長した。IQKA irradiates pulsed electrons i with a pulse width of 5 ns to excite the reaction gas in the reactor 101. At the same time, the low-pressure mercury lamp 103 is turned on and ultraviolet light is irradiated perpendicularly to the substrate 108 to excite the surface of the substrate 108. A silicon nitride film was grown on top.
以上の様にして形成した窒化硅素膜の膜質を密度、バッ
フアート弗酸に対するエツチング速度。The quality of the silicon nitride film formed as described above is determined by its density and etching rate with respect to buffered hydrofluoric acid.
電流−電圧特性、容量−電圧特性から評価し、通常のプ
ラズマ化学気相成長による窒化硅素膜と比較したところ
、上記評価において格段に優れた特性を示した。When evaluated from the current-voltage characteristics and capacitance-voltage characteristics and compared with a silicon nitride film produced by ordinary plasma chemical vapor deposition, it showed significantly superior characteristics in the above evaluation.
すなわち、密度は３．０１ ｇ／Ｃｍ３と高く、エツチ
ング速度は０．３ ｎｍ／ｍ ｉ ｎと小さく、電界強
度２ＭＶ／ｃｍでのリーク′シ流は２ ×ｌ ＯＡ／
ｃｍ２＋界面電荷密度は２ Ｘ １０−１０−１Ｏ”と
低い値であった。That is, the density is high at 3.01 g/Cm3, the etching rate is low at 0.3 nm/min, and the leakage current at an electric field strength of 2 MV/cm is 2 × l OA/cm.
The cm2+ interfacial charge density was as low as 2 x 10-10-1 O''.
このように本発明の化学気相成長法によ）形成した窒化
硅素膜は通常のプラズマ化学気相成長による窒化硅素膜
に比べより緻密で電気的特性の優れた膜であった。また
、成長速腿も１００ ｎ Ｉｌｌ／ｍ １ ｎと通常の
光化学気相成長法に比べ約十倍の大きさである。As described above, the silicon nitride film formed by the chemical vapor deposition method of the present invention was denser and had better electrical characteristics than a silicon nitride film formed by ordinary plasma chemical vapor deposition. Furthermore, the growth rate is 100 nIll/m 1 n, which is about ten times as fast as that of ordinary photochemical vapor deposition.
第２図は本発明の第２の実施例を説明するための装置の
縦断面図である。反応炉２０１．を子線加速器２０２．
ヒータ２０３．ガス導入口２０４゜ガス排出口２０５．
基板２０６．原料ガスボンベ２０７、電界を生じさせる
ためのグリッド２０８゜サセプター２０９を備えている
。FIG. 2 is a longitudinal sectional view of an apparatus for explaining a second embodiment of the present invention. Reactor 201. The particle accelerator 202.
Heater 203. Gas inlet 204° Gas outlet 205.
Substrate 206. It is equipped with a raw material gas cylinder 207, a grid 208 for generating an electric field, and a susceptor 209.
次にこの装置を用いてアルミニウム膜を形成することと
し、その手順について述べる。基板２０６をヒータ２０
３上に設置し設定温度に加熱する。Next, this apparatus will be used to form an aluminum film, and the procedure will be described. The substrate 206 is connected to the heater 20
3 Place it on top and heat it to the set temperature.
原料ガスＡｌ（ＣＨ３）ｓを導入し、反応炉２０１内の
圧力が１Ｔｏｒｒ程度の定常流で安定したところで、グ
リッド２０８とサセプター２０９との間に静電場ｅ加、
ｔ、０．５ＭｅＶ、１０ＫＡ 、パｈス幅５ｎｓのパル
ス電子線を電子線加速器２０２より照射して、アルミニ
ウム膜成長を行った。After introducing the raw material gas Al(CH3)s and stabilizing the pressure inside the reactor 201 at a steady flow of about 1 Torr, an electrostatic field e is applied between the grid 208 and the susceptor 209.
A pulsed electron beam of 0.5 MeV, 10 KA, and a path width of 5 ns was irradiated from an electron beam accelerator 202 to grow an aluminum film.
以上の様にして形成したアルミニウム膜は抵抗２．４μ
Ωｃｍと通常のスパッタ膜と同程度の値であった。かつ
、二次イオン質量分析の結果から炭素等不純物が混入し
ていないことがわかった３、さらに、走査型電子顕微鏡
で表面観察したところ、ヒロックや粒界等の成長のない
表面モホロジーの優扛た金属機であった。また、グリッ
ド２０８とサセプター２０９との間に印加する電圧を０
−１ｋＶと変化させたところ、２００Ｖできわめて段差
被羨件のすぐれた膜が得られた。このとき成長速度は最
大となＦ）１２０ｎｍ／ｍｉｎであった。The aluminum film formed as described above has a resistance of 2.4μ.
The value was Ωcm, which was comparable to that of a normal sputtered film. In addition, the results of secondary ion mass spectrometry revealed that no impurities such as carbon were mixed in. Furthermore, when the surface was observed using a scanning electron microscope, it was found that the surface morphology was excellent, with no growth of hillocks or grain boundaries. It was a metal machine. Also, the voltage applied between the grid 208 and the susceptor 209 is set to 0.
When the voltage was changed to -1kV, a film with extremely high level difference resistance was obtained at 200V. At this time, the growth rate was maximum, F) 120 nm/min.
以上説明したように本発明は、パルス寛子線照射し反応
ガスを電離することにより、無損傷の薄膜形成を低温に
て高速度で行うことができる効果がある。As explained above, the present invention has the effect of being able to form a damage-free thin film at a low temperature and at a high speed by ionizing a reactive gas by irradiating a pulsed Hiroton beam.
第１図は本発明の第１の実施例に用いる化学気相成長装
置の断面図、第２図は本発明の第２の実施例に用いる化
学気相成長装置の断面図である。
１０１・・・・・・反応炉、１０２・・・・・・電子線
加速器、１０３・・・・・・低圧水銀灯、１０４・・・
・・・合成石英窓、１０５゛・°・°°上ヒータ１０６
・・・・・・ガス導入口、１０７・・・・・・ガス排気
口、１０８・・・・・・基板、１０９，１１０・・・・
・・原料ガスボンベ、２０１・パ・°°反応炉、２０２
・・・・・・電子線加速器、２０３・・・・・・ヒータ
、２０４・・・・・・ガス導入口、２０５・・・・・・
ガス排出口、２０６・・・°°°基板、２０７”°゛°
゛°原料ガスボンベ、２０８・・・・・・グリッド、２
ｏ９・・・・・・サセプター。FIG. 1 is a sectional view of a chemical vapor deposition apparatus used in a first embodiment of the invention, and FIG. 2 is a sectional view of a chemical vapor deposition apparatus used in a second embodiment of the invention. 101... Reactor, 102... Electron beam accelerator, 103... Low pressure mercury lamp, 104...
...Synthetic quartz window, 105゛・°・°°upper heater 106
...Gas inlet, 107...Gas exhaust port, 108...Substrate, 109, 110...
・・Raw material gas cylinder, 201・Pa・°°reactor, 202
...Electron beam accelerator, 203...Heater, 204...Gas inlet, 205...
Gas outlet, 206...°°° Board, 207"°°
゛°Raw material gas cylinder, 208...Grid, 2
o9... Susceptor.
Claims (4)
ス電子線を照射して基板上に膜形成を行なうことを特徴
とする化学気相成長法。(1) A chemical vapor deposition method characterized in that a reactive gas is used as a raw material and a film is formed on a substrate by irradiating the reactive gas with a pulsed electron beam.
に照射することを特徴とする特許請求の範囲第１項記載
の化学気相成長法。(2) The chemical vapor deposition method according to claim 1, wherein the pulsed electron beam is irradiated onto the reaction gas and the substrate.
記基板に紫外線を照射した状態で行うことを特徴とする
特許請求の範囲第１項記載の化学気相成長法。(3) The chemical vapor deposition method according to claim 1, wherein the pulsed electron beam is irradiated onto the reaction gas while the substrate is irradiated with ultraviolet rays.
基板に向かう静電場が形成された状態で、行なわれるこ
とを特徴とする特許請求の範囲第１項記載の化学気相成
長法。(4) The chemical vapor deposition method according to claim 1, wherein the pulsed electron beam is irradiated onto the reaction gas while an electrostatic field directed toward the substrate is formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6657687A JPS63232338A (en) | 1987-03-19 | 1987-03-19 | Chemical vapor phase epitaxy method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6657687A JPS63232338A (en) | 1987-03-19 | 1987-03-19 | Chemical vapor phase epitaxy method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63232338A true JPS63232338A (en) | 1988-09-28 |
Family
ID=13319918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6657687A Pending JPS63232338A (en) | 1987-03-19 | 1987-03-19 | Chemical vapor phase epitaxy method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63232338A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100147807A1 (en) * | 2008-12-15 | 2010-06-17 | Samsung Electronics Co., Ltd. | Electron beam annealing apparatuses and annealing methods using the same |
-
1987
- 1987-03-19 JP JP6657687A patent/JPS63232338A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100147807A1 (en) * | 2008-12-15 | 2010-06-17 | Samsung Electronics Co., Ltd. | Electron beam annealing apparatuses and annealing methods using the same |
| US8445366B2 (en) * | 2008-12-15 | 2013-05-21 | Samsung Electronics Co., Ltd. | Electron beam annealing apparatus and annealing methods using the same |
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