JPS6313343B2 - - Google Patents
Info
- Publication number
- JPS6313343B2 JPS6313343B2 JP56036382A JP3638281A JPS6313343B2 JP S6313343 B2 JPS6313343 B2 JP S6313343B2 JP 56036382 A JP56036382 A JP 56036382A JP 3638281 A JP3638281 A JP 3638281A JP S6313343 B2 JPS6313343 B2 JP S6313343B2
- Authority
- JP
- Japan
- Prior art keywords
- silicon
- film
- substrate
- vapor deposition
- nitrogen compound
- 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
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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
- C23C16/44—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
- C23C16/505—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 radio frequency discharges
- C23C16/509—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 radio frequency discharges using internal electrodes
- C23C16/5096—Flat-bed apparatus
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Description
【発明の詳細な説明】
本発明は化学気相成長方法に係り、特に珪素の
窒素化合物（ここにいう珪素の窒素化合物とは、
窒化珪素及びシリコン・オキシ・ナイトライド等
をいう）の化学気相成長方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a chemical vapor deposition method, and particularly relates to a silicon nitrogen compound (silicon nitrogen compound referred to here).
This invention relates to a method for chemical vapor deposition of silicon nitride, silicon oxy nitride, etc.).
半導体集積回路装置等に於ては、素子表面の保
護絶縁膜として窒化珪素（SixNy）或るいはシリ
コン・オキシ・ナイトライド（SixOzNy）等の
珪素の窒素化合物皮膜が用いられ、これら珪素の
窒素化合物からなる表面保護膜は、被形成基板上
に既に形成されているアルミニウム（Al）配線
等の変質を避けるために、低温に於て高成長速度
が得られるプラズマ化学気相成長方法により一般
に形成される。 In semiconductor integrated circuit devices, silicon nitrogen compound films such as silicon nitride (SixNy) or silicon oxy nitride (SixOzNy) are used as protective insulating films on the element surfaces. In order to avoid deterioration of aluminum (Al) wiring, etc. that has already been formed on the substrate, the surface protective film is generally formed by plasma chemical vapor deposition, which can achieve a high growth rate at low temperatures. Ru.
そして珪素の窒素化合物のプラズマ化学気相成
長に際して珪素（Si）原子を提供する成長ガスの
成分としては、従来からモノシラン（SiH4）が
用いられており、窒化珪素（SixNy）膜を形成す
る際には、SiH4に例えばアンモニア・ガス
（NH3）が附加され、該成長ガスに於てはシラン
の分解が完全に行なわれないために水素を含んだ
窒化珪素（Si−Ｎ−Ｈ）が形成される。そして珪
素（Si）と水素（Ｈ）の結合は弱いために、該窒
化珪素膜（Si−Ｎ−Ｈ）に温度がかかつた場合、
Ｈが離脱して該窒化珪素膜にクラツクや剥れ等の
欠陥が生じ、素子表面の保護絶縁効化が低下する
という問題、或るいは該窒化珪素膜に含まれる水
素原子Ｈが電界に引かれて素子表面に近い界面に
集るために、該水素原子による寄生電荷のため
に、半導体素子の特性が変化するという問題等が
あつた。 Monosilane (SiH 4 ) has traditionally been used as a component of the growth gas that provides silicon (Si) atoms during plasma chemical vapor deposition of silicon nitrogen compounds, and when forming silicon nitride (SixNy) films, In this method, for example, ammonia gas (NH 3 ) is added to SiH 4 , and since silane is not completely decomposed in the growth gas, silicon nitride (Si-N-H) containing hydrogen is formed. It is formed. Since the bond between silicon (Si) and hydrogen (H) is weak, when the silicon nitride film (Si-N-H) is heated,
The problem is that hydrogen atoms H are released and defects such as cracks and peeling occur in the silicon nitride film, reducing the protective insulation effectiveness of the element surface, or hydrogen atoms H contained in the silicon nitride film are attracted to an electric field. Since hydrogen atoms gather at the interface near the device surface, there is a problem that the characteristics of the semiconductor device change due to parasitic charges caused by the hydrogen atoms.
本発明は上記問題点を除去する目的で、水素原
子の含有量が極めて少ない珪素の窒素化合物を、
プラズマ化学気相成長により形成する方法を提供
する。 In order to eliminate the above-mentioned problems, the present invention uses a silicon nitrogen compound with an extremely low hydrogen atom content.
A method of forming the present invention by plasma enhanced chemical vapor deposition is provided.
即ち本発明は、化学気相成長方法に於て、ハロ
ゲン化珪素と窒素化合物或るいは窒素を含む成長
ガスを用い、該成長ガスをプラズマ中で化学反応
せしめて、被処理基体上に窒化珪素（SixNy）、
シリコン・オキシ・ナイトライド（SixOzNy）
等の珪素の窒素化合物からなる皮膜を形成せしめ
ることを特徴とする。 That is, the present invention uses a growth gas containing silicon halide and a nitrogen compound or nitrogen in a chemical vapor deposition method, and causes the growth gas to undergo a chemical reaction in plasma to form silicon nitride on a substrate to be processed. (SixNy),
Silicon oxy nitride (SixOzNy)
It is characterized by forming a film made of a silicon nitrogen compound such as.
以下本発明を、一実施例について、図に示すプ
ラズマ化学気相成長装置の断面模式図及び第２図
に示す本発明を適用して表面保護膜を形成した半
導体素子の一例に於ける断面構造図を用いて詳細
に説明する。 The present invention will be described below with reference to one embodiment, a schematic cross-sectional view of a plasma chemical vapor deposition apparatus shown in the figure, and a cross-sectional structure of an example of a semiconductor element in which a surface protective film is formed by applying the present invention shown in FIG. This will be explained in detail using figures.
本発明の化学気相成長方法に用いるプラズマ化
学気相成長（CVD）装置は通常の構造を有して
おり、例えば第１図に示すように、真空排気管１
ａ，１ｂ及び成長ガス導入管２を有する基台３上
に、パツキン４を介して気密を保つてベルジヤー
５がかぶせられており、該ベルジヤー５内に形成
される成長室内に於ける基台３上に加熱装置６を
内蔵し、且つ中央にガス流通孔７を有する基板保
持台８が設けられており、該基板保持台８の上面
と所望の距離をへだてた位置に、該基板保持台８
の上面と平行な対向電極９が配設されてなつてい
る。そして前記対向電極９は高周波発振器RFを
経て接地Ｇされており、又前記基板保持台８も基
台３を介して接地Ｇされる。 The plasma chemical vapor deposition (CVD) apparatus used in the chemical vapor deposition method of the present invention has a normal structure, for example, as shown in FIG.
A bell gear 5 is placed on the base 3 having the growth gas inlet pipe 2 and the growth gas introduction tube 2 through a gasket 4 to maintain airtightness. A substrate holder 8 is provided with a built-in heating device 6 on the top and a gas flow hole 7 in the center.
A counter electrode 9 is disposed parallel to the upper surface of. The counter electrode 9 is grounded via a high frequency oscillator RF, and the substrate holding table 8 is also grounded via the base 3.
本発明の方法を用いて表面保護用の窒化珪素
（SixNy）膜を形成するには、例えば前記第１図
に示すようなプラズマCVD装置の基板保持台上
に、機能領域やアルミニウム（Al）配線等の形
成が終つた半導体集積回路基板等の被処理基板１
０を載置し、成長ガス導入管２からアルゴン
（Ar）或るいは窒素（N2）等のパージ・ガスを
流入し、真空排気管１ａ及び１ｂから排気を行つ
て、成長室内を前記パージ・ガスで置換する。次
いで被処理基板１０を350〜400〔℃〕に昇温せし
めて後、成長ガス導入管２から、例えば１〜10
〔％〕程度の四弗化珪素（SiF4）を含んだArガス
（ArベースSiF4）及び該SiF4に対してモル比率で
３／４〔倍〕以上の三弗化窒素（NF3）を混合した
成長ガスを所望の流量で導入し、前記真空排気管
１ａ及び１ｂから所望の排気量で排気を行つて、
成長室内の成長ガス圧を例えば１〔Torr〕近辺に
調整する。次いで基板保持台８と対向電極９間
に、例えば13.56〔ＭHz〕10〜100〔Ｗ〕程度の高周
波電力を印加し、被処理基板１０と対向電極９間
にプラズマを発生せしめ、所望の時間維持して、
被処理基板１０上に例えば0.1〜１〔μm〕程度の
SixNy膜を成長せしめる。 In order to form a silicon nitride (SixNy) film for surface protection using the method of the present invention, for example, on the substrate holder of a plasma CVD apparatus as shown in FIG. A substrate 1 to be processed, such as a semiconductor integrated circuit board, etc., which has been formed.
0, a purge gas such as argon (Ar) or nitrogen (N 2 ) is introduced from the growth gas introduction pipe 2, and exhaust is performed from the vacuum exhaust pipes 1a and 1b to fill the growth chamber with the purge gas.・Replace with gas. Next, after raising the temperature of the substrate to be processed 10 to 350 to 400 [°C], for example, 1 to 10
Ar gas (Ar-based SiF 4 ) containing about [%] silicon tetrafluoride (SiF 4 ) and nitrogen trifluoride (NF 3 ) at a molar ratio of 3/4 [times] or more to the SiF 4 A growth gas mixed with is introduced at a desired flow rate, and is evacuated from the vacuum exhaust pipes 1a and 1b at a desired amount,
The growth gas pressure in the growth chamber is adjusted to around 1 [Torr], for example. Next, high frequency power of about 13.56 [MHz] 10 to 100 [W], for example, is applied between the substrate holding table 8 and the counter electrode 9 to generate plasma between the substrate to be processed 10 and the counter electrode 9 and maintain it for a desired time. do,
For example, a layer of about 0.1 to 1 [μm] is formed on the substrate 10 to be processed.
Grow SixNy film.
又本発明の方法を用いてシリコン・オキシ・ナ
イトライド（SixOzNy）膜を形成する際には、
上記成長ガスに更に前記NF3に対して５〜10〔％〕
程度の小量の一酸素化二窒素（N2O）を加えて、
上記同様の方法で成長させればよい。 Furthermore, when forming a silicon oxy nitride (SixOzNy) film using the method of the present invention,
In addition to the above growth gas, 5 to 10% of the NF3 is added.
Adding a small amount of dinitrogen monooxygenate (N 2 O) to
It may be grown using the same method as above.
上記実施例の方法に於ては、珪素の窒素化合物
を化学気相成長せしめる成長ガス中に水素原子
（Ｈ）が含まれていない。従つて成長せしめられ
た珪素の窒素化合物即ち（SixNy），（SixOzNy）
等の膜はＨを含有せず、且つ反応の際に生成する
活性化された弗素原子（Ｆ）と上記珪素の窒素化
合物とが強固に結合して、高温に於てクラツク等
の発生がない極めて安定なSi−Ｆ−Ｎ或るいはSi
−Ｆ−Ｏ−Ｎ構造を有する膜が形成される。 In the method of the above embodiment, hydrogen atoms (H) are not contained in the growth gas for chemical vapor deposition of silicon nitrogen compounds. Therefore, the grown silicon nitrogen compounds, i.e. (SixNy), (SixOzNy)
These films do not contain H, and the activated fluorine atoms (F) generated during the reaction are strongly bonded to the silicon nitrogen compound, so that no cracks occur at high temperatures. Extremely stable Si-F-N or Si
A film having a -F-O-N structure is formed.
第２図は上記実施例の方法を用いて表面保護絶
縁膜を形成したMIS型半導体素子の一例の断面構
造図で、図に於て１１はシリコン基板、１２はフ
イールド絶縁膜、１３はチヤネル・カツト領域、
１４はソース領域、１５はドレイン領域、１６は
ゲート酸化膜、１７はゲート配線、１８はソース
配線、１９はドレイン配線、２０はカバー用りん
珪酸ガラス（PSG）膜、２１は1000Å程度の厚
さを有する珪素の窒素化合物膜、２２は下層絶縁
膜を示している。 FIG. 2 is a cross-sectional structural diagram of an example of a MIS type semiconductor device in which a surface protection insulating film is formed using the method of the above embodiment. In the figure, 11 is a silicon substrate, 12 is a field insulating film, and 13 is a channel. cut area,
14 is a source region, 15 is a drain region, 16 is a gate oxide film, 17 is a gate wiring, 18 is a source wiring, 19 is a drain wiring, 20 is a phosphosilicate glass (PSG) film for a cover, and 21 is a thickness of about 1000 Å. 22 indicates a lower insulating film.
このような構造を有せしめた半導体素子に於て
は、本発明の方法で形成したカバー用PSG膜２
０上を覆う珪素の窒素化合物膜２１は、前記
PSG膜２０に比べ格段にすぐれた耐湿性を有し
ている。そして前述のように高温に於てクラツク
等の発生することのない極めて安定なSi−Ｆ−Ｈ
或るいはSi−Ｆ−Ｏ−Ｎ膜となつているので、該
素子をパツケージにろう付けする際、或るいはパ
ツケージをシールする際等の高温処理に於ても該
珪素の窒素化合物膜にクラツクが発生することが
なく、素子表面は湿気から完全に保護される。又
前述のように該珪素の窒素化合物膜には水素原子
（Ｈ）が含まれないので、寄生電荷が生ずること
がなく、素子特性が安定する。 In a semiconductor device having such a structure, a PSG film 2 for a cover formed by the method of the present invention is used.
The silicon nitrogen compound film 21 covering the
It has much better moisture resistance than PSG film 20. And as mentioned above, Si-F-H is extremely stable and does not cause cracks at high temperatures.
Alternatively, since the film is a Si-F-O-N film, the silicon nitrogen compound film is No cracks occur and the element surface is completely protected from moisture. Further, as described above, since the silicon nitrogen compound film does not contain hydrogen atoms (H), parasitic charges are not generated, and device characteristics are stabilized.
上記実施例に於ては、本発明の成長ガスのSi成
分としてSiF4を用いたが、該Si成分として四塩化
珪素（SiCl4）等のハロゲン化珪素を用いても同
様の効果が得られる。 In the above example, SiF 4 was used as the Si component of the growth gas of the present invention, but the same effect can be obtained by using a silicon halide such as silicon tetrachloride (SiCl 4 ) as the Si component. .
以上説明したように本発明の方法によれば、耐
湿性に優れ、且つ高温に於て安定な表面保護膜が
形成できるので、半導体装置の製造歩留まりや信
頼性を向上させることができる。 As explained above, according to the method of the present invention, a surface protective film that has excellent moisture resistance and is stable at high temperatures can be formed, so that the manufacturing yield and reliability of semiconductor devices can be improved.
第１図は本発明の一実施例に使用したプラズマ
化学気相成長装置の断面模式図で、第２図は本発
明を適用して表面保護膜を形成した半導体素子の
一例に於ける断面構造図である。
図に於て、１ａ及び１ｂは真空排気管、２は成
長ガス導入管、３は基台、４はパツキン、５はベ
ルジヤー、６は加熱装置、７はガス流通孔、８は
基板保持台、９は対向電極、１０は被処理基板、
１１はシリコン基板、１２はフイールド絶縁膜、
１３はチヤネル・カツト領域、１４はソース領
域、１５はドレイン領域、１６はゲート酸化膜、
１７はゲート配線、１８はソース配線、１９はド
レイン配線、２０はカバー用りん珪酸ガラス膜、
２１は珪素の窒素化合物膜、２２は下層絶縁膜、
RFは高周波発振器、Ｇは接地を示す。
FIG. 1 is a schematic cross-sectional view of a plasma chemical vapor deposition apparatus used in an embodiment of the present invention, and FIG. 2 is a cross-sectional structure of an example of a semiconductor element in which a surface protective film is formed by applying the present invention. It is a diagram. In the figure, 1a and 1b are vacuum exhaust pipes, 2 is a growth gas introduction pipe, 3 is a base, 4 is a gasket, 5 is a bell gear, 6 is a heating device, 7 is a gas flow hole, 8 is a substrate holding table, 9 is a counter electrode, 10 is a substrate to be processed,
11 is a silicon substrate, 12 is a field insulating film,
13 is a channel cut region, 14 is a source region, 15 is a drain region, 16 is a gate oxide film,
17 is a gate wiring, 18 is a source wiring, 19 is a drain wiring, 20 is a phosphosilicate glass film for a cover,
21 is a silicon nitrogen compound film, 22 is a lower insulating film,
RF indicates a high frequency oscillator, and G indicates ground.
Claims (1)
含む成長ガスを用い、該成長ガスをプラズマ中で
化学反応せしめて、被処理基体上に珪素の窒素化
合物からなる皮膜を形成せしめることを特徴とす
る化学気相成長方法。1. It is characterized by using silicon halide and a nitrogen compound or a growth gas containing nitrogen, and causing the growth gas to undergo a chemical reaction in plasma to form a film made of a silicon nitrogen compound on the substrate to be treated. Chemical vapor deposition method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3638281A JPS57152132A (en) | 1981-03-13 | 1981-03-13 | Chemical vapor growing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3638281A JPS57152132A (en) | 1981-03-13 | 1981-03-13 | Chemical vapor growing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57152132A JPS57152132A (en) | 1982-09-20 |
| JPS6313343B2 true JPS6313343B2 (en) | 1988-03-25 |
Family
ID=12468291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3638281A Granted JPS57152132A (en) | 1981-03-13 | 1981-03-13 | Chemical vapor growing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57152132A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5279448A (en) * | 1975-12-25 | 1977-07-04 | Toyota Motor Corp | Fixing device for tiltable handwheel |
| JPS5996736A (en) * | 1982-11-26 | 1984-06-04 | Hitachi Ltd | Semiconductor device |
| JPS61145834A (en) * | 1984-12-20 | 1986-07-03 | Toshiba Corp | Manufacture of semiconductor device |
| JPS61256735A (en) * | 1985-05-10 | 1986-11-14 | Nec Corp | Semiconductor device and manufacture thereof |
| JPS62166530A (en) * | 1986-01-20 | 1987-07-23 | Toshiba Corp | Manufacture of semiconductor device |
| JP2659193B2 (en) * | 1987-08-20 | 1997-09-30 | 日本電気株式会社 | Semiconductor device |
-
1981
- 1981-03-13 JP JP3638281A patent/JPS57152132A/en active Granted
Non-Patent Citations (1)
| Title |
|---|
| SOLID-STATE SCIENCE AND TECHNOLOGY=1977 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57152132A (en) | 1982-09-20 |
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