JPH0239593B2 - - Google Patents
Info
- Publication number
- JPH0239593B2 JPH0239593B2 JP59046839A JP4683984A JPH0239593B2 JP H0239593 B2 JPH0239593 B2 JP H0239593B2 JP 59046839 A JP59046839 A JP 59046839A JP 4683984 A JP4683984 A JP 4683984A JP H0239593 B2 JPH0239593 B2 JP H0239593B2
- Authority
- JP
- Japan
- Prior art keywords
- sif
- silicon
- silicon nitride
- gas
- plasma
- 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
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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
-
- 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)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Plasma & Fusion (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Description
【発明の詳細な説明】
この発明は、プラズマ化学反応を用いた気相反
応方法（以下CVD法という）により弗素が添加
された窒化珪素、例えば光フアイバー用のコーテ
イング、また半導体エレクトロニクス用のパツシ
ベイシヨン被膜を作製する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to silicon nitride doped with fluorine by a gas phase reaction method using a plasma chemical reaction (hereinafter referred to as CVD method), for example, coatings for optical fibers, and passivation coatings for semiconductor electronics. This invention relates to a method for producing a .
この発明は弗素が低級に添加され（HnSim ｍ
＝１，２，３）Si−Ｆ結合を有するとともに、低
い放電エネルギでプラズマCVD法を実施するこ
とにより被形成面をスパツタすることなく窒化珪
素を作製する方法に関する。 In this invention, fluorine is added to a low level (HnSim m
= 1, 2, 3) This invention relates to a method of producing silicon nitride having Si--F bonds and without sputtering the surface on which it is formed by performing a plasma CVD method with low discharge energy.
この発明は珪素の弗素化物と窒素または窒素の
水素化物とを反応せしめ、窒化珪素被膜を500℃
以下の温度好ましくは100〜400℃例えば300℃で
形成する方法に関する。 This invention involves reacting silicon fluoride with nitrogen or nitrogen hydride to form a silicon nitride film at 500°C.
It relates to a method of forming at the following temperature, preferably 100 to 400°C, for example 300°C.
従来、窒化珪素膜を作製せんとするのは、グロ
ー放電法を用いたプラズマ気相反応方法によりシ
ラン（SiH4）とアンモニア（NH3）とを反応せ
しめ、200〜400℃の基板温度にて被膜を作製して
いた。しかしかかる窒化珪素膜は、その膜内に珪
素の不対結合手、珪素のクラスタが残存すること
により残留電荷を生ずる。そしてこの電荷のため
に、MOS.IC等のフアイナル・コーテイングとし
て用いることができなかつた。 Conventionally, silicon nitride films have been produced by reacting silane (SiH 4 ) and ammonia (NH 3 ) using a plasma vapor phase reaction method using a glow discharge method at a substrate temperature of 200 to 400°C. A film was being made. However, such a silicon nitride film generates residual charges due to residual silicon dangling bonds and silicon clusters remaining within the film. Because of this charge, it could not be used as a final coating for MOS.IC, etc.
さらに、この方法においては、生成された酸化
珪素中にクラスタおよびOHを残存してしまう。
このため実用上において水素をまつたく用いない
窒化珪素被膜を作製する方法が求められていた。 Furthermore, in this method, clusters and OH remain in the produced silicon oxide.
For this reason, there has been a need for a method for producing a silicon nitride film that does not use hydrogen in practical applications.
本発明はかかる目的のため、即ち珪素の弗素化
物であるHnSiFm（ｍ＝１，２，３，ｎ＝０〜３
即ちSiF2，H2SiF2，HSF3，H3SiF）特に好まし
くはSiF2を用いることにより窒化珪素を作製せん
とするものである。 The present invention is intended for such purpose, namely, HnSiFm (m=1,2,3, n=0-3), which is a silicon fluoride.
Specifically, silicon nitride is produced by using SiF 2 , H 2 SiF 2 , HSF 3 , H 3 SiF, and particularly preferably SiF 2 .
その主たる反応式は 3SiF2＋2N2H4−Si3N4＋6HF＋H2である。 The main reaction formula is 3SiF 2 +2N 2 H 4 -Si 3 N 4 +6HF+H 2 .
このため低級弗素化珪物気体としてSiF2を用い
た。 For this reason, SiF 2 was used as the lower fluorinated silicate gas.
以下に図面に従つて本発明を記す。 The present invention will be described below with reference to the drawings.
第１図は本発明に用いられたCVD装置の概要
を示す。 FIG. 1 shows an outline of the CVD apparatus used in the present invention.
図面において、反応容器（真空容器）１は石英
からなつている。基板２はヒータ３で囲まれた石
英管１内に配設され、好ましくは200〜400℃例え
ば300℃に加熱がされている。ドーピング系は流
量計６，バルブ７よりなり、アンモニアまたは窒
素は１０より供給される。ヒドラジン（N2H4）
（MP1.4℃，BP113.5℃）は室温で液体であるた
め、バブラ２０に充填されている。このヒドラジ
ンは無水を用い、さらにモレキユラシーブ２１に
より超高純度に除湿精製した。また、珪素の弗素
化物は１１より供給される。珪素の弗素化物
（SiF2とSiF4の混合物）は８よりSiFが供給され、
石英管内の金属珪素（純度9N以上）１７をヒー
タ１５により100〜1250℃に加熱してSiF2を以下
の式のごとくにして作製した。このSiF2の製造方
法に関してはJ.ELectrochem.Soc.（1981）p2660
〜2665に示されている方法を用いた。 In the drawing, a reaction vessel (vacuum vessel) 1 is made of quartz. The substrate 2 is placed in a quartz tube 1 surrounded by a heater 3, and preferably heated to 200-400°C, for example 300°C. The doping system consists of a flow meter 6 and a valve 7, and ammonia or nitrogen is supplied from 10. Hydrazine ( N2H4 )
(MP1.4°C, BP113.5°C) is a liquid at room temperature, so it is filled in the bubbler 20. This hydrazine was anhydrous and further dehumidified and purified using Molecular Sieve 21 to ultra-high purity. Further, silicon fluoride is supplied from 11. Silicon fluoride (mixture of SiF 2 and SiF 4 ) is supplied with SiF from 8,
Metallic silicon (purity 9N or higher) 17 in a quartz tube was heated to 100 to 1250°C using a heater 15 to produce SiF 2 according to the following formula. Regarding the manufacturing method of SiF 2 , see J.ELectrochem.Soc. (1981) p2660.
~2665 was used.
SiF4＋Si→2SiF2
これらの反応性気体（実際にはSiF2とSiF4との
混合気体）を１１より反応容器内に導入し、さら
に排気口７より圧力調整バルブ１２、ストツプバ
ルブ１３をへて、真空ポンプ１４より排気させ
た。プラズマ化学反させる電気エネルギ供給装置
５が設けられている。この高周波エネルギ供給用
コイル４を囲んで抵抗加熱ヒータ３が設けられて
いる。 SiF 4 +Si→2SiF 2These reactive gases (actually a mixed gas of SiF 2 and SiF 4 ) are introduced into the reaction vessel from 11, and then passed through the pressure adjustment valve 12 and stop valve 13 from the exhaust port 7. , and was evacuated from the vacuum pump 14. An electrical energy supply device 5 for plasma chemical reaction is provided. A resistance heater 3 is provided surrounding this high frequency energy supply coil 4.
以下にその実施例を示す。 Examples are shown below.
実施例
この実施例はSiF2とアンモニアとのプラズマ気
相反応により窒化珪素被膜を単結晶珪素基板上に
作製した。Example In this example, a silicon nitride film was formed on a single crystal silicon substrate by a plasma vapor phase reaction between SiF 2 and ammonia.
用いた装置を第１図に示す。基板温度は300℃、
圧力0.7torr、電気エネルギ（13.56MHz）の供給
により反応性気体をプラズマ化（プラズマ密度
0.3mW／cm2）した。 The apparatus used is shown in Figure 1. The substrate temperature is 300℃,
The reactive gas is turned into plasma (plasma density
0.3mW/cm 2 ).
この窒化珪素上に対抗電極を作り、ダイオード
構造として、Ｃ−Ｖ特性を測定した。その結果、
界面準位密度は３×1011cm-2以下であつて、酸化
珪素被膜は直流電界を加えた場合、１×106V／
cmにおいて初めてヒステリシス特性が観察され、
珪素基板上に形成された酸化珪素中に珪素クラス
タの存在により電荷捕獲中心が少ないことが判明
した。 A counter electrode was formed on this silicon nitride to form a diode structure, and the CV characteristics were measured. the result,
The interface state density is 3×10 11 cm -2 or less, and the silicon oxide film has a voltage of 1×10 6 V/cm when a DC electric field is applied.
Hysteresis characteristics were observed for the first time in cm,
It was found that there are fewer charge trapping centers due to the presence of silicon clusters in silicon oxide formed on a silicon substrate.
即ち、本発明方法のSiFn（ｎ＝１，２，３一般
にはｎ＝２）と窒素もしくは窒化物気体（NH3，
N2H4，NF3）との反応方法は半導体のパツシベ
イシヨン膜としてきわめて有効であることが判明
した。この実施例においては、MIS.FFTのゲイ
ト絶縁膜として有効であり、それぞれを用途によ
り使い分けるとよいことが判明した。 That is, in the method of the present invention, SiFn (n=1, 2, 3, generally n=2) and nitrogen or nitride gas (NH 3 ,
It has been found that the reaction method with N 2 H 4 , NF 3 ) is extremely effective as a passivation film for semiconductors. In this example, it was found that it is effective as a gate insulating film for MIS.FFT, and that it is better to use each film depending on the purpose.
本発明において、プラズマCVD法に加えて
300nm以下の光エネルギの照射を同時に併用して
実施してもよいことはいうまでもない。 In the present invention, in addition to the plasma CVD method,
It goes without saying that irradiation with light energy of 300 nm or less may be carried out simultaneously.
第１図は本発明方法を実施するためのCVD装
置の概要を示す。
FIG. 1 shows an outline of a CVD apparatus for carrying out the method of the present invention.
Claims (1)
される珪素の弗素化物気体と窒素化物気体との混
合反応性気体に電気エネルギーを加えることによ
り、プラズマを発生させて500℃以下の温度で被
形成面上に弗素が添加された窒化珪素の半導体用
保護膜を作製することを特徴とする窒化珪素作製
方法。Plasma is generated by applying electrical energy to a mixed reactive gas of silicon fluoride gas and nitride gas represented by 1 H o SiF n (m = 1, 2, 3, n = 0 to 3). A method for manufacturing silicon nitride, characterized in that a protective film for a semiconductor of silicon nitride doped with fluorine is manufactured on a surface to be formed at a temperature of 500° C. or less.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4683984A JPS60190564A (en) | 1984-03-12 | 1984-03-12 | Preparation of silicon nitride |
| US06/710,111 US4704300A (en) | 1984-03-12 | 1985-03-11 | Method for producing silicon nitride layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4683984A JPS60190564A (en) | 1984-03-12 | 1984-03-12 | Preparation of silicon nitride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60190564A JPS60190564A (en) | 1985-09-28 |
| JPH0239593B2 true JPH0239593B2 (en) | 1990-09-06 |
Family
ID=12758506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4683984A Granted JPS60190564A (en) | 1984-03-12 | 1984-03-12 | Preparation of silicon nitride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60190564A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5861086A (en) * | 1997-03-10 | 1999-01-19 | Applied Materials, Inc. | Method and apparatus for sputter etch conditioning a ceramic body |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62174927A (en) * | 1986-01-28 | 1987-07-31 | Nec Corp | Semiconductor device |
| CA2706215C (en) | 2010-05-31 | 2017-07-04 | Corrosion Service Company Limited | Method and apparatus for providing electrochemical corrosion protection |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6047202B2 (en) * | 1976-01-13 | 1985-10-21 | 東北大学金属材料研究所長 | Super hard high purity oriented polycrystalline silicon nitride |
| JPS6057507B2 (en) * | 1981-10-20 | 1985-12-16 | 日本重化学工業株式会社 | Manufacturing equipment and method for manufacturing ultra-hard high-purity silicon nitride |
| JPS58115011A (en) * | 1982-12-27 | 1983-07-08 | Res Inst Iron Steel Tohoku Univ | Amorphous silicone nitride having high hardnes and high purity and its preparation |
-
1984
- 1984-03-12 JP JP4683984A patent/JPS60190564A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5861086A (en) * | 1997-03-10 | 1999-01-19 | Applied Materials, Inc. | Method and apparatus for sputter etch conditioning a ceramic body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60190564A (en) | 1985-09-28 |
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