JP2638446B2 - Method for manufacturing protective film - Google Patents
Method for manufacturing protective filmInfo
- Publication number
- JP2638446B2 JP2638446B2 JP5287934A JP28793493A JP2638446B2 JP 2638446 B2 JP2638446 B2 JP 2638446B2 JP 5287934 A JP5287934 A JP 5287934A JP 28793493 A JP28793493 A JP 28793493A JP 2638446 B2 JP2638446 B2 JP 2638446B2
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- protective film
- film
- surfactant
- group
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electrodes Of Semiconductors (AREA)
- Formation Of Insulating Films (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、半導体装置等のＳｉや
Ａｌが表面に存在する基材表面に保護膜を形成する方法
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a protective film on a surface of a substrate such as a semiconductor device on which Si or Al exists.
【０００２】[0002]
【従来の技術】従来の半導体装置の製造プロセスにおい
ては、バイポーラ、ＭＯＳ素子などに関わらず、アルミ
電極形成後、素子を、水やアルカリ金属から保護し、あ
るいは外部から物理的にも保護するために、リンガラ
ス、シリコン窒化膜などを保護膜として形成する必要が
あった。2. Description of the Related Art In a conventional semiconductor device manufacturing process, after an aluminum electrode is formed, the element is protected from water or alkali metal, or physically protected from the outside, regardless of whether the element is bipolar or MOS. In addition, it was necessary to form a protective film such as a phosphor glass or a silicon nitride film.
【０００３】例えば、バイポーラ構造のＩＣ製造の際に
は、常圧下にて、ＰＳＧ膜を厚さ約３０００Å形成後、
減圧下にて、プラズマＳｉ−Ｎ膜（窒化シリコン膜）を
厚さ約５０００Å形成している。For example, when manufacturing an IC having a bipolar structure, a PSG film having a thickness of about 3000 mm is formed under normal pressure.
Under reduced pressure, a plasma Si—N film (silicon nitride film) is formed to a thickness of about 5000 °.
【０００４】[0004]
【発明が解決しようとする課題】従来の保護膜形成にお
いては、温度や圧力を制御しながら、ＣＶＤ装置・プラ
ブマ装置などを用いて行う必要があった。従って、ウェ
ハーのスループット量が装置の性能に大きく依存してい
た。In the conventional method of forming a protective film, it was necessary to control the temperature and the pressure while using a CVD apparatus or a plasma apparatus. Therefore, the throughput of the wafer greatly depends on the performance of the apparatus.
【０００５】また、プラズマＳｉ3 Ｎ4 膜については、
その膨張率がＳｉＯ2 に比べ高すぎるために、Ａｌ配線
に対してストレス・マイグレーションを引き起こし、素
子の電気的特性を悪化することもあった。[0005] Regarding the plasma Si 3 N 4 film,
Since the coefficient of expansion is too high as compared with SiO 2 , stress migration may be caused on the Al wiring, and the electrical characteristics of the device may be deteriorated.
【０００６】本発明は上述のような、従来の問題点に鑑
み、安価に量産性良く、均一で安定な保護膜を得ること
を目的とする。The present invention has been made in view of the above-described conventional problems, and has as its object to obtain a uniform and stable protective film at a low cost and with good productivity.
【０００７】[0007]
【課題を解決するための手段】本発明は、Ａｌ等の電極
形成後のＳｉ基板の表面で、フッ化炭素基または炭化水
素基とクロロシリル基を含むシラン系界面活性剤を吸着
反応させて前記界面活性剤よりなる化学吸着単分子膜を
共有結合を介して基材表面に結合形成することを特徴と
した保護膜の製造方法である。According to the present invention, a silane-based surfactant containing a fluorocarbon group or a hydrocarbon group and a chlorosilyl group is adsorbed and reacted on the surface of an Si substrate after an electrode such as Al is formed. A method for producing a protective film, characterized in that a chemically adsorbed monomolecular film made of a surfactant is bonded to a substrate surface through a covalent bond.
【０００８】[0008]
【作用】本発明は、化学吸着法を用いるため、シラン系
化学吸着単分子膜がきわめて強力な共有結合を介して基
板表面に結合形成でき、Ａｌ等の電極形成後のＳｉ基板
表面全面にわたり保護膜を非常に簡単な装置で、単分子
レベルの厚さで超高密度に薄く形成できる。According to the present invention, since a chemisorption method is used, a silane-based chemisorption monomolecular film can be bonded to the substrate surface through an extremely strong covalent bond, and can be protected over the entire surface of the Si substrate after forming an electrode such as Al. The film can be formed at a very high density with a very simple device at a thickness of a single molecule.
【０００９】[0009]
【実施例】以下、本発明の一実施例について、図面に基
づき詳しく説明する。図１に示す第１の実施例では、例
えば、図１（ａ）に示すように、従来のプロセス技術に
より、Ａｌ電極形成後のバイポーラＩＣ等が形成された
Ｓｉ基板１を常備する。このとき、基板１の表面には、
ＳｉＯ2 ２やＡｌ３（Ｓｉを含有する場合もある）が、
パターン状に形成されている。そこで、図１（ｂ）に示
すように、化学吸着法により、炭化水素基とクロロシリ
ル基を含むシラン界面活性剤（例えば、ＣＨ 2 ＝ＣＨ−
（ＣＨ2 ）n −ＳｉＣｌ3 （ｎは整数で、１０〜３０が
良い。なお、炭化水素基であるＣＨ2 ＝ＣＨ−は、ＣＨ
＝Ｃ−でも良い。）を用い、基板１の表面で吸着反応さ
せ、BRIEF DESCRIPTION OF THE DRAWINGS FIG.
This will be described in detail. In the first embodiment shown in FIG.
For example, as shown in FIG.
Thus, a bipolar IC or the like after the formation of the Al electrode was formed.
An Si substrate 1 is always provided. At this time, the surface of the substrate 1
SiOTwo2 and Al3 (which may contain Si)
It is formed in a pattern. Therefore, as shown in FIG.
As described above, hydrocarbon groups and chlorosilyl
Silane surfactant containing a thiol group (eg, CH Two= CH-
(CHTwo)n-SiClThree(N is an integer and 10 to 30
good. In addition, CH which is a hydrocarbon groupTwo= CH- is CH
= C-. ), The adsorption reaction on the surface of the substrate 1
Let
【００１０】[0010]
【化１】 Embedded image
【００１１】の化学吸着単分子膜４を形成する。例え
ば、２．０×１０-3〜５．０×１０-2ｍｏｌ／ｌの濃度
で溶した８０％ｎ−セタン、１２％四塩什炭素、８％ク
ロロホルム溶媒中に浸漬すると、図１（ｃ）に示すよう
に、基板１の表面でThe chemically adsorbed monomolecular film 4 is formed. For example, when immersed in a solvent of 80% n-cetane, 12% tetrachlorotetracarbon and 8% chloroform dissolved at a concentration of 2.0 × 10 −3 to 5.0 × 10 −2 mol / l, FIG. As shown in c), on the surface of the substrate 1
【００１２】[0012]
【化２】 Embedded image
【００１３】の結合５を形成する。ここでは、シラン界
面活性剤の各分子は、基板１上にて分子レベルで密度高
く配列されている。この単分子膜４は、非常に高い疎水
性を示すので、膜４を含んで基板１の表面は、図１
（ｄ）に示すように、外部からの水分子６に対して、非
常に高い疎水性を示すことになる。なお、この実施例で
はＨ 2 Ｃ＝ＣＨ−基を酸化することにより、同じ方法を
くり返して多層の単分子膜を形成することも可能とな
る。The bond 5 is formed. Here, the silane world
Each molecule of the surfactant has a high density at the molecular level on the substrate 1.
Well arranged. This monomolecular film 4 has a very high hydrophobicity.
The surface of the substrate 1 including the film 4 is shown in FIG.
As shown in (d), the water molecules 6 from outside are
It will always show high hydrophobicity. In this example,
Is H TwoBy oxidizing the C = CH- group,
It is also possible to form multiple monolayers by repeating
You.
【００１４】第２の実施例では、第１の実施例にて使用
した単分子膜４の代わりに、分子末端にフッ素を持つ、
フルオロシラン界面活性剤、例えば、In the second embodiment, instead of the monomolecular film 4 used in the first embodiment, fluorine is present at the molecular terminal.
Fluorosilane surfactants, for example,
【００１５】[0015]
【化３】 Embedded image
【００１６】（ｎは整数で、１０〜３０が良い。）を用
い、第１の実施例と同様の工程を行い、図２（ａ）に示
すように、基板１の表面で吸着反応させ、化学吸着単分
子膜４を形成する。ここで、単分子膜４は、図２（ｂ）
に示すように、膜４の表面で、Using (n is an integer, preferably 10 to 30), the same steps as in the first embodiment are performed, and as shown in FIG. The chemical adsorption monomolecular film 4 is formed. Here, the monomolecular film 4 is formed as shown in FIG.
As shown in the figure, on the surface of the film 4,
【００１７】[0017]
【化４】 Embedded image
【００１８】の結合６を密度高く配列させている。一般
に、−ＣＦ3 基は炭化水素基よりも高い疎水性を有し、
かつ、分子全体の耐摩耗性も高くなるので、この工程に
より、膜２を含んで基板１の表面は、外部に対して非常
に高い疎水性を示し、かつ、高い耐摩耗性を示す。The bonds 6 are arranged at high density. Generally, -CF 3 groups have high hydrophobicity than a hydrocarbon group,
In addition, since the wear resistance of the whole molecule also becomes high, the surface of the substrate 1 including the film 2 exhibits extremely high hydrophobicity to the outside and high wear resistance by this step.
【００１９】[0019]
【発明の効果】以上のように本発明によれば、溶液への
浸漬方法による化学吸着を用い、シラン界面活性剤より
なる疎水性の単分子膜を共有結合を介して基材表面に結
合形成するため、基板に形成された段差をもつＩＣ等表
面にＳｉやＡｌを含む基材の表面全面に亘り分子レベル
の膜厚で、くまなく膜が強固に形成される。よって、Ｓ
ｉやＡｌを含む基材表面の安定な保護膜としての効果は
絶大である。また、本発明方法に必要な装置も、簡単か
つ安価なものなので、安定かつ強固な保護膜の製造コス
トも削減でき、基材表面処理のスリープット量も大幅に
増加できる。As described above, according to the present invention, a hydrophobic monomolecular film composed of a silane surfactant is formed on the surface of a substrate through a covalent bond by using chemical adsorption by a method of immersion in a solution. As a result, the film is firmly formed all over the surface of an IC or the like having a step formed on the substrate at a molecular level over the entire surface of the substrate containing Si or Al. Therefore, S
The effect as a stable protective film on the substrate surface containing i and Al is enormous. Further, since the apparatus required for the method of the present invention is simple and inexpensive, the production cost of a stable and strong protective film can be reduced, and the amount of sleep required for substrate surface treatment can be greatly increased.
【図１】（ａ）〜（ｄ）は本発明の一実施例方法を説明
するための工程概念図である。1 (a) to 1 (d) are process conceptual diagrams for explaining a method of one embodiment of the present invention.
【図２】（ａ）、（ｂ）は本発明の他の実施例を説明す
るための概念図である。FIGS. 2A and 2B are conceptual views for explaining another embodiment of the present invention.
１ 基板 ２ Ａｌ ３ ＳｉＯ2 ４ 単分子膜 ５、７ 結合 ６ 水分子1 substrate 2 Al 3 SiO 2 4 monolayer 5,7 bond 6 water molecules
Claims (2)
でフッ化炭素基または炭化水素基とクロロシリル基を含
むシラン系界面活性剤を吸着反応させて前記界面活性剤
よりなる化学吸着単分子膜を共有結合を介して基材表面
に結合形成することを特徴とした保護膜の製造方法。A silane-based surfactant containing a fluorinated carbon group or a hydrocarbon group and a chlorosilyl group is adsorbed on the surface of a substrate of a semiconductor device containing Si or Al to form a chemisorption unit comprising the surfactant. A method for producing a protective film, comprising forming a molecular film on a substrate surface through a covalent bond.
基を含み他端にクロロシリル基を含む界面活性剤を用い
ることを特徴とした請求項１記載の保護膜の製造方法。2. A silane surfactant having --CF 3 at one end.
The method for producing a protective film according to claim 1, wherein a surfactant containing a chlorosilyl group at the other end is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5287934A JP2638446B2 (en) | 1993-11-17 | 1993-11-17 | Method for manufacturing protective film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5287934A JP2638446B2 (en) | 1993-11-17 | 1993-11-17 | Method for manufacturing protective film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62158225A Division JPH0622227B2 (en) | 1987-06-25 | 1987-06-25 | Semiconductor device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06342787A JPH06342787A (en) | 1994-12-13 |
| JP2638446B2 true JP2638446B2 (en) | 1997-08-06 |
Family
ID=17723630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5287934A Expired - Lifetime JP2638446B2 (en) | 1993-11-17 | 1993-11-17 | Method for manufacturing protective film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2638446B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102480348B1 (en) * | 2018-03-15 | 2022-12-23 | 삼성전자주식회사 | Pre-treatment composition before etching SiGe and method of fabricating a semiconductor device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62145532A (en) * | 1985-12-18 | 1987-06-29 | Nec Corp | Magnetic memory medium and its production |
-
1993
- 1993-11-17 JP JP5287934A patent/JP2638446B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06342787A (en) | 1994-12-13 |
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