JPH03266426A - Formation of molybdenum pattern - Google Patents
Formation of molybdenum patternInfo
- Publication number
- JPH03266426A JPH03266426A JP6436290A JP6436290A JPH03266426A JP H03266426 A JPH03266426 A JP H03266426A JP 6436290 A JP6436290 A JP 6436290A JP 6436290 A JP6436290 A JP 6436290A JP H03266426 A JPH03266426 A JP H03266426A
- Authority
- JP
- Japan
- Prior art keywords
- film
- sputtering
- deposited
- molybdenum
- etching
- 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 23
- 239000011733 molybdenum Substances 0.000 title claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 239000007789 gas Substances 0.000 claims abstract description 62
- 238000004544 sputter deposition Methods 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052754 neon Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005530 etching Methods 0.000 abstract description 33
- 238000001039 wet etching Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 230000006835 compression Effects 0.000 abstract 4
- 238000007906 compression Methods 0.000 abstract 4
- 230000005596 ionic collisions Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 75
- 239000000758 substrate Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 210000000554 iris Anatomy 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002128 reflection high energy electron diffraction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
- ing And Chemical Polishing (AREA)
- Electrodes Of Semiconductors (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用公費〉
本発明は、モリブデンパタンの形成方法に関し、モリブ
デンパタンを形成するに際し、特に段差被覆性に優れた
テーパ加工を施すことができるように工夫したものであ
る。[Detailed Description of the Invention] <Industrial Utilization Public Expenses> The present invention relates to a method for forming a molybdenum pattern, and is devised so that taper processing with particularly excellent step coverage can be performed when forming the molybdenum pattern. It is something.
〈従来の技術〉
一般にモリブデン（Ｍｏ）等の高融点金属膜は、ＬＳＩ
等の半導体集積回路や薄膜トランジスタ（ＴＰＴ）等を
用いた薄膜デバイスのゲート電極材料や配線材料として
広く用いられている。<Prior art> Generally, high melting point metal films such as molybdenum (Mo) are used in LSI
It is widely used as a gate electrode material or wiring material for semiconductor integrated circuits such as , thin film devices using thin film transistors (TPT), etc.
従来においては、Ｍｏ等の高融点金属膜の形成の際アル
ゴン（Ａｒ）をスパッタガスとして用い、スパッタ法で
堆積すると、選択配向を示し基板に垂直な柱状組織（Ｃ
ｏｌｕ■ｎｅｒＳｔｒｕｅｔｕｒｅ）が形成されるため
、配線パタンに加工するとパタンエツジが、この構造を
反映して垂直ないしオーバハング状となる欠点があった
。Conventionally, when forming a high melting point metal film such as Mo, argon (Ar) is used as a sputtering gas and when deposited by sputtering, a columnar structure (C
Since this structure is formed, when processed into a wiring pattern, the pattern edges become vertical or overhanging, reflecting this structure.
これは、Ａｒをスパッタガスとして用いてＭｏ膜を形成
する場合、体心立方格子（ｂｅｅ）の金属膜を堆積する
と、最稠密面（１１０）を基板に平行とした＜１１０＞
配向のＭｏ膜が得られることに起因している。すなわち
この最稠密面（１１０）は、最も原子密度の高い面で、
エツチング速度が小さいことが知られているので、Ａｒ
で堆積した＜１１０＞配向のＭｏ膜では、最稠密な（１
１０）面が表面および等砥面として垂直な面とに現れる
ため、上記した膜構造と共に垂直なエツチング形状が生
じたと考えられる。When forming a Mo film using Ar as a sputtering gas, when depositing a body-centered cubic lattice (bee) metal film, the closest packed plane (110) is parallel to the substrate <110>
This is due to the fact that an oriented Mo film is obtained. In other words, this most densely packed plane (110) is the plane with the highest atomic density,
Since the etching speed is known to be low, Ar
In the <110> oriented Mo film deposited at
10) Since the plane appears on the surface and the perpendicular plane as a uniformly polished plane, it is thought that a vertical etched shape was generated together with the above-mentioned film structure.
このため、Ｍｏパタン上に絶縁膜を堆積し、２層目配線
を形成する場合、Ｍｏパタンのパタンエツジ上の絶縁膜
ないし２層目配線の段差被覆性が悪く、絶縁不良や２層
目配線の断線を生じ易い欠点があった。For this reason, when depositing an insulating film on the Mo pattern to form a second layer wiring, the step coverage of the insulating film on the pattern edge of the Mo pattern or the second layer wiring is poor, resulting in poor insulation and the formation of the second layer wiring. There was a drawback that wire breakage was likely to occur.
この問題を解決する方法として、本発明者らは、先に特
開昭６１−１７０５６１号公報（特願昭６０−１１０７
６号）において、ネオン（Ｎｅ）をスパッタガスに用い
て、＜１１１＞配向したＭｏ膜を形成する方法を提案し
た。As a method to solve this problem, the present inventors previously published Japanese Patent Application Laid-Open No. 170561/1982 (Japanese Patent Application No. 1107/1982).
No. 6) proposed a method of forming a <111> oriented Mo film using neon (Ne) as a sputtering gas.
本方法は、Ｎｅをスパッタガスに用い、１Ｐａす上の高
ガス圧側でＭｏ膜の堆積を行うと、＜１１１＞配向のＭ
ｏ膜が得られることを開示するものである。すなわち、
＜１１１＞配向Ｍｏ膜では、エツチング速度の遅い最稠
密面が基板に対し斜めに存在するため、従来のようなＡ
ｒで堆積した＜１１０＞配向Ｍｏ膜と加工特性が異なる
ため、反応性ドライエツチング法でテーパ状に加工する
ことが可能となった。In this method, when a Mo film is deposited at a high gas pressure of 1 Pa using Ne as a sputtering gas, the <111> oriented M
It is disclosed that an o film can be obtained. That is,
In the <111> oriented Mo film, the closest packed plane with a slow etching rate exists obliquely to the substrate, so the conventional A
Since the processing characteristics are different from those of the <110> oriented Mo film deposited by r, it became possible to process it into a tapered shape using the reactive dry etching method.
〈発明が解決しようとする課題〉
しかしながら、上述したＮｏをスパッタガスとして用い
てＩＰｍ以上のガス圧で得られた＜１１１＞配向Ｍｏ膜
の加工特性を詳細に調へてみると、反応性ドライエツチ
ング法では、上述したようにテーパ加工は可能であるが
、過酸化水素水（Ｈ２０□）を用いた簡易なウェットエ
ツチング法では、過剰にエツチングを行わないと（いわ
ゆるオーバーエツチング）１良好なテーパ加工特性を示
さず、エツチング時間の設定や形状のコントロールが難
しいという欠点が生じている。<Problems to be Solved by the Invention> However, when we examine in detail the processing characteristics of the <111> oriented Mo film obtained using the above-mentioned No as a sputtering gas at a gas pressure of IPm or higher, we find that the reactive drying With the etching method, taper processing is possible as described above, but with the simple wet etching method using hydrogen peroxide (H20□), if excessive etching is not performed (so-called over-etching), a good taper cannot be obtained. The drawback is that it does not exhibit any processing characteristics, and it is difficult to set the etching time and control the shape.
本発明は以上述べた亭情に艦み、ウェットエツチング法
で制御性よく良好なテーパ加工可能なモリブデンパタン
の形成方法を提供することを目的とする。In view of the above-mentioned circumstances, it is an object of the present invention to provide a method for forming a molybdenum pattern that can be tapered with good controllability using a wet etching method.
く課題を解決するための手段〉
前記目的を達成するために本発明者らは鋭意研究を重ね
た結果、Ｎｏをスパッタガスとして堆積したＭｏ膜の構
造を調べて行くと、１Ｐａ以上のガス圧では前述したよ
うに明瞭なく１１１＞配向を示すが、１Ｐａ未満ではア
モルファス相を含んだ＜１１０＞配向のＭ。Means for Solving the Problems In order to achieve the above object, the inventors of the present invention have conducted extensive research, and as a result of investigating the structure of a Mo film deposited using No as a sputtering gas, it was found that a gas pressure of 1 Pa or higher was found. As mentioned above, M clearly shows the 111> orientation, but at less than 1 Pa, the M has the <110> orientation including an amorphous phase.
膜が得られることを知見した。さらにこの１Ｐａ未満の
低ガス圧側で堆積した＜１１０＞配向のＭｏ膜は、ジャ
ストエツチングで約４５゜以下のテーパ角の加工ができ
ることも知見した。It was found that a film could be obtained. Furthermore, it has been found that a <110> oriented Mo film deposited at a low gas pressure of less than 1 Pa can be processed to a taper angle of about 45° or less by just etching.
本発明は、上記知見に基づくもので、従来技術が＜１１
１＞配向を使用するのに対し、本発明は＜１１１＞配向
ではなく、アモルファス相を含む＜１１０＞配向を用い
る点が異なり、エツチング終了判定が容易なジャストエ
ツチングで良好なテーパ加工可能な本発明に係るモリブ
デンパタンの形成方法を完成した。The present invention is based on the above knowledge, and the conventional technology is <11
1> orientation, whereas the present invention uses a <110> orientation containing an amorphous phase rather than a <111> orientation, and the present invention is different in that it uses a <110> orientation that includes an amorphous phase, and it is possible to perform a good taper process by just etching, which makes it easy to determine the end of etching. A method for forming a molybdenum pattern according to the invention has been completed.
かかる本発明のモリブデンパタンの形成方法の構成は、
スパッタ法により堆積したモリブデン膜をパタン化する
モリブデン膜の形成方法において、圧縮応力状態下にモ
リブデン膜を堆積した後、過酸化水素水を用いて加工す
ることを特徴とする。The structure of the method for forming a molybdenum pattern of the present invention is as follows:
A method for forming a molybdenum film in which a molybdenum film deposited by sputtering is patterned is characterized in that the molybdenum film is deposited under compressive stress and then processed using hydrogen peroxide solution.
息下、本発明の詳細な説明する。The present invention will now be described in detail.
本発明で、圧縮応力状態下にモリブデン膜（Ｍｏ膜）を
堆積するとは、スパッタガスとして例えばＮｅを用い、
このスパッタガスのガス圧を１Ｐａ以下の低ガス圧条件
にて、Ｍ。In the present invention, depositing a molybdenum film (Mo film) under a compressive stress state means using, for example, Ne as a sputtering gas,
The gas pressure of this sputtering gas was set to 1 Pa or less under low gas pressure conditions.
膜を堆積させると、該Ｍｏ膜の内部応力が圧縮応力を示
すように堆積していくことをいう。This means that when a film is deposited, the internal stress of the Mo film exhibits compressive stress.
ここでスパッタガスとしては上記Ｎｅに限定されず、Ｎ
ｏを主成分としたガスに例えばＡｒ、Ｋｒ、Ｘｓ、Ｒｎ
等の不活性ガスを混合し？：ｗ！ｉ合ガスを用いてもよ
い。この場合の混合比は、Ｎｏ／Ｎｅ十不活性ガスの比
率が７０％す上とするのが好ましい。Here, the sputtering gas is not limited to the above Ne, but is N
For example, Ar, Kr, Xs, Rn, etc.
Mix inert gas such as? :w! i gas may also be used. In this case, the mixing ratio is preferably 70% or more of No/Ne and inert gas.
乙のようにＭｏ膜を圧縮応力状態下に堆積すると、反跳
イオンの衝突により、スパッタ膜特有の柱状構造が崩さ
れ、膜の内部にアモルファス相を生じ、このアモルファ
ス相の工、チング速度が遅いエツチング法を用いること
により、従来技術では容易でなかったＭｏ膜のテーパエ
ツチングが可能となる。When a Mo film is deposited under compressive stress as shown in Part 2, the columnar structure peculiar to the sputtered film is destroyed by the collision of recoil ions, creating an amorphous phase inside the film, and the processing and ching rate of this amorphous phase increases. By using the slow etching method, taper etching of the Mo film, which was not easy with the prior art, becomes possible.
このアモルファス相を含むＭｏ膜をスパッタ法で簡易に
形成するには、上述したように反跳イオンの衝撃を増加
させスパッタ膜特有の柱状構造を壊せばよい。このよう
にすると、膜の応力は当然圧縮状態になる。すなわち、
アモルファス相の存在と圧縮応力とは表裏一体の関係に
ある。この状態を実現するには、低質量のスパッタガス
を用いるのがよい。In order to easily form a Mo film containing this amorphous phase by sputtering, the columnar structure peculiar to the sputtered film can be destroyed by increasing the impact of recoil ions as described above. In this way, the stress in the film naturally becomes compressive. That is,
The existence of an amorphous phase and compressive stress are two sides of the same coin. To achieve this condition, it is preferable to use a low mass sputtering gas.
また、基板に負のバイアスを印加し、反跳イオンを基板
方向に加速し、散乱の効果を取り除いても良いことは明
らかである。It is also obvious that a negative bias may be applied to the substrate to accelerate the recoil ions toward the substrate to remove the scattering effect.
本発明では、スパッタガスとして上述したようにＮｏを
主として用いるが、これは後述する実施例で示すように
、容易に圧縮応力のＭｏ膜が得られるとともに、膜堆積
速度がＡｒの嘘程度で実用的なためと、バイアス印加が
不用で装置改造を伴うことなく実行できる実用上の利点
があるためである。In the present invention, No is mainly used as the sputtering gas as described above, but as shown in the examples described later, it is easy to obtain a Mo film with compressive stress, and the film deposition rate is about the same as that of Ar, making it practical. This is because it has the practical advantage of not requiring bias application and requiring no equipment modification.
エツチング液としては、本発明では過酸化水素水を用い
るが、アモルファス相のエツチング速度が小さければよ
く、本発明はこれに限定されるものではない。As the etching solution, hydrogen peroxide solution is used in the present invention, but the present invention is not limited to this as long as the etching rate of the amorphous phase is low.
く実 施 例〉
つぎに、実施例及び比較例に基づいて、本発明の内容を
具体的に説明する。EXAMPLES Next, the content of the present invention will be specifically explained based on Examples and Comparative Examples.
［実施例１］
５インチ×１５インチの高周波（ＲＦ）プレナマグネト
ロン電極を有するスパッタ装置により、Ｍｏ膜を堆積し
た。Example 1 A Mo film was deposited using a sputtering device with a 5 inch x 15 inch radio frequency (RF) planar magnetron electrode.
使用装置は円筒形の基板ホルダを持ち、基板ホルダは装
置中央を回転軸として回転する。The device used has a cylindrical substrate holder, and the substrate holder rotates around the center of the device as an axis of rotation.
したがって、基板ホルダ上の基板には、基板がターゲッ
ト近傍を通過する時Ｍｏ膜が堆積される。ターゲットと
基板とは対向位置で５０閣である。Therefore, a Mo film is deposited on the substrate on the substrate holder when the substrate passes near the target. The target and the board are in opposing positions at 50 degrees.
また、ターゲットには９９．９％以上のＭ。In addition, the target contains M of 99.9% or more.
板を用いた。基板には０．１μｍの熱酸化膜を形成した
（１００）Ｓｉウェハを用いた。スパッタガスには高純
度Ｎｏを用いた。A board was used. A (100) Si wafer on which a 0.1 μm thermal oxide film was formed was used as the substrate. High purity No was used as the sputtering gas.
上記装置を用い、約２ｘｌＯＰａ以下に真空排気したの
ち、スパッタガスＮｅを導入し、スパッタ電力２ Ｋ
Ｗで膜厚的１００ ｎｍのＭ。Using the above equipment, after evacuation to approximately 2xlOPa or less, sputtering gas Ne was introduced and the sputtering power was 2K.
M with a film thickness of 100 nm using W.
膜を堆積した。A film was deposited.
このような条件下で、スパッタリングのガス圧を変化さ
せて、菖々のＭｏ膜を堆積し、それらに過酸化水素水を
用いてウェットエツチング法でエツチングし、それらの
断面形状を調べた。Under such conditions, the sputtering gas pressure was varied to deposit irises of Mo films, which were then etched by wet etching using hydrogen peroxide solution to examine their cross-sectional shapes.
この結果、スパッタリングのガス圧が１Ｐａ未満の低ガ
ス圧側では、ジャストエツチング条件で約４５°以下の
テーパ角を示す良−好なテーパ加工ができ、さらにオー
バエツチングを行なうとテーパ角が低下していった。As a result, on the low gas pressure side of sputtering gas pressure of less than 1 Pa, good taper processing with a taper angle of approximately 45° or less can be achieved under just etching conditions, and when overetching is performed, the taper angle decreases. It was.
一方、スパッタリングのガス圧が１Ｐａ以上の高ガス圧
側では、従来と同様＜１１１＞配向を示し、エツチング
が丁度終了するジャストエツチング条件では断面が垂直
になるが、更にエツチングを進めてゆくと徐々にテーパ
状になっていき、ジャストエツチングの約倍のオーバエ
ツチングを行なうとテーパ状になった。On the other hand, when the sputtering gas pressure is on the high gas pressure side of 1 Pa or more, it shows the <111> orientation as before, and under the just-etching conditions where etching has just finished, the cross section becomes vertical, but as the etching progresses further, it gradually changes. It gradually became tapered, and when overetching was performed about twice as much as just etching, it became tapered.
第１図はスパッタガス圧Ｐと後に述べる膜の内部応力σ
の関係を示したもので、図中にジャストエツチング条件
でのＭｏパタン断面形状の模式図を示す。Ｎｏをスパッ
タガスとして用いた場合、Ｍｏ膜の圧縮応力を示す領域
でテーパ加工が得られているのが分かる。Figure 1 shows the sputtering gas pressure P and the internal stress σ of the film, which will be described later.
The figure shows a schematic diagram of the cross-sectional shape of a Mo pattern under just etching conditions. It can be seen that when No is used as the sputtering gas, taper processing is obtained in the region of the Mo film exhibiting compressive stress.
本実施例で得られたＮｏで堆積したＭｏ膜の構造を反射
高速電子線回折（ＲＩｌ［ＥＥＤ）で調べてみると、前
述したように低ガス圧で堆積したＭｏ膜は、＜１１０＞
配向を示す回折パタンとともにアモルファス相を示すハ
ローが重畳しているのに対し、高ガス圧で堆積したＭ。When the structure of the Mo film deposited with No obtained in this example was investigated by reflection high-energy electron diffraction (RII [EED)], it was found that the Mo film deposited at low gas pressure had <110>
While the halo indicating the amorphous phase is superimposed on the diffraction pattern indicating the orientation, M deposited under high gas pressure.
膜は＜１１１＞配向を示す回折パタンが明瞭に見られる
ことが分かった。It was found that the film had a clearly visible diffraction pattern indicating <111> orientation.
一方、膜の内部応力を測定すると、低ガス圧で堆積した
Ｍｏ膜は大きな圧縮応力を示すが、高ガス圧で堆積した
Ｍｏ膜では引っ張り応力となっていることが分かった。On the other hand, when measuring the internal stress of the film, it was found that the Mo film deposited at low gas pressure showed large compressive stress, but the Mo film deposited at high gas pressure showed tensile stress.
上記実施例でテーパ加工が生じた領域では、第１図に示
したように圧縮応力が一様に見られた。In the region where the taper process occurred in the above example, compressive stress was uniformly observed as shown in FIG.
一般に、スパッタ膜では文献（Ｊ、人、Ｔｈｏｒａｔｏ
ｎａｎｄ Ｄ、Ｗ、Ｈｏｆｆｍａｎ、 ”Ｉｎｔｅｒｎ
ａｌ ５ｔｒｅｓｓｅｓ １ｎｔｉｔ亀ｎｉｕｍ、ｎ１
ｅｋｅ１．ｍｏｌｙｂｄｅｎｕｍ、ａｎｄ を亀ｎｔ
ａｌｕｍｆｉ１ｍｓ ｄｅｐｏｓｉｔｅｄ ｂｙ ｅｙ
ｌｉｎｄｒｉｃａｌ ｍａｇｎｅｔｒｏｎｓｐｕｔｔｅ
ｒｉｎｇ 、 Ｊ、Ｖａｃ、Ｓｃｉ、Ｔｅｅｈｎｏｌ
、、ｖｏｌ、１４ｐ、 １６４−１８８８．１９７７）
に示されているように、スパッタガス圧を変えてゆくと
、低ガス圧で圧縮応力となり、高ガス圧になると引っ張
り応力となることが分かっている。また、スパッタガス
の質量が小さいほど圧縮応力から引っ張り応力になる転
移ガス圧が大きくなる。In general, sputtered films are described in the literature (J.
and D., W. Hoffman, “Intern.
al 5tresses 1ntit turtlenium, n1
eke1. molybdenum, and
alumfi1ms deposited by ey
lindrical magnetronsputte
ring, J., Vac., Sci., Teehnol.
,, vol, 14p, 164-1888.1977)
As shown in , it is known that when the sputtering gas pressure is changed, compressive stress occurs at low gas pressures, and tensile stress occurs at high gas pressures. Furthermore, the smaller the mass of the sputtering gas, the greater the transition gas pressure that changes from compressive stress to tensile stress.
これは、ターゲットに衝突したスパッタイオンが反跳し
て堆積膜と衝突することにより構造が変化するピーニン
グ（釘打ち）効果として説明されている。This is explained as a peening effect in which sputtered ions that collide with the target recoil and collide with the deposited film, resulting in a structural change.
すなわち、低ガス圧では反跳イオンがスパッタガスによ
る散乱を受けず、高エネルギを保持したまま基板表面に
衝突するため、構造が変形を受は緻密化され圧縮応力状
態となるのに対し、高ガス圧では反跳イオンがスパッタ
ガスの散乱効果によりエネルギが減速されるため有効に
基板に衝突しないため、蒸着膜と同様引っ張り応力のま
まとなる。特に、スパッタガスの質量が小さいと散乱に
よるエネルギ低下の割合が小さく、転移ガス圧が上昇す
ると考えられる。In other words, at low gas pressure, recoil ions are not scattered by the sputtering gas and collide with the substrate surface while retaining high energy. At gas pressure, the energy of the recoil ions is slowed down by the scattering effect of the sputtering gas, so they do not effectively collide with the substrate, so they remain under tensile stress like the deposited film. In particular, it is thought that when the mass of the sputtering gas is small, the rate of energy reduction due to scattering is small and the transition gas pressure increases.
本実施例で示したＮｏで堆積したＭｏ膜は、上記傾向に
一致し、第１図に示すように、低ガス圧で堆積したＭｏ
膜は圧縮応力を示し、スパッタガス圧が上昇すると引っ
張り応力になる。さらに、低ガス圧では反跳イオンの衝
突により構造が崩され、アモルファス相を生じたものと
推定゛される。The Mo film deposited with No shown in this example corresponds to the above tendency, and as shown in FIG.
The film exhibits compressive stress, which becomes tensile stress as the sputtering gas pressure increases. Furthermore, it is presumed that at low gas pressures, the structure is destroyed by collisions of recoil ions, resulting in an amorphous phase.
このため、過酸化水素水でのエツチングでは上記アモル
ファス相の存在により、等方性エツチングを生じ、テー
パ加工可能となったと考えられる。For this reason, it is thought that due to the presence of the amorphous phase, isotropic etching occurs during etching with hydrogen peroxide solution, making taper processing possible.
一方、先に出願した特開昭６１−１７０５６１号公報（
特願昭６０−１１０７６号）に示した反応性ドライエツ
チングでは、アモルファス相のエツチング速度が大きく
、配向特性を示す骨格を形成する部分がエツチング形状
を支配するため、＜１１０＞配向を示す低ガス圧領域で
はテーパエツチングができなかったと推定される。On the other hand, the previously filed Japanese Patent Application Laid-open No. 170561/1983 (
In the reactive dry etching shown in Japanese Patent Application No. 60-11076, the etching rate of the amorphous phase is high, and the part forming the skeleton exhibiting orientation characteristics dominates the etched shape. It is presumed that taper etching was not possible in the pressure region.
次に、本実施例１と同様の装置を用い、Ｎ。Next, using the same apparatus as in Example 1, N.
のスパッタガス圧が０．５Ｐｉ及びＡｒのスパッタガス
圧が０．５ＰＪｌの条件で各々Ｍｏ膜を堆積し、過酸化
水素水を用いたウェットエツチング法のジャストエツチ
ング条件でエツチングを終了した各々のＭｏパタン上に
、スパッタ法で二酸化シリコン（Ｓ ｉ Ｏ２）膜を堆
積した上で、加熱した過酸化水素とアンモニア水の混合
液に浸漬した。Each Mo film was deposited under the conditions of a sputtering gas pressure of 0.5 Pi and an Ar sputtering gas pressure of 0.5 PJl, and etching was completed under the just etching conditions of the wet etching method using hydrogen peroxide solution. A silicon dioxide (S i O 2 ) film was deposited on the pattern by sputtering, and then immersed in a heated mixture of hydrogen peroxide and aqueous ammonia.
この結果、 Ｎｅの水準ではＳ ｉ Ｏ２膜下のＭ。As a result, at the level of Ne, M under the SiO2 film.
膜のエツチングは全く生じなかったのに対し、Ａｒの水
準ではＭｏ膜がパタンエツジから過酸化水素水でエツチ
ングされた。No film etching occurred at all, whereas at the Ar level, the Mo film was etched from the pattern edge with hydrogen peroxide solution.
これは、Ｎｏで堆積したＭｏ膜ではテーパ加工によすｓ
ｉｏ、膜が均一に堆積されＭｏ膜を完全に覆うことがで
きたが、Ａｒではパタンエツジが垂直ないしオーバハン
グ状になるためＳ ｉ ＯＩの被覆性が悪く、薄い部分
から過酸化水素が侵入し、Ｍｏ膜がエツチングされたこ
とによる。This is due to taper processing in the Mo film deposited with No.
io, the film was deposited uniformly and was able to completely cover the Mo film, but with Ar, the pattern edges were vertical or overhanging, so the coverage of SiOI was poor, and hydrogen peroxide entered from the thin part. This is due to the Mo film being etched.
すなわち、Ｎｅで堆積したＭｏ膜はテーパ加工できるこ
とから、その上に形成する膜の被覆性を改善する効果が
あった。That is, since the Mo film deposited with Ne can be tapered, it has the effect of improving the coverage of the film formed thereon.
［実施例２］
本実施例は上記実施例とは方式の異なるスパッタ装置で
Ｍｏ膜を堆積したものである。[Example 2] In this example, a Mo film was deposited using a sputtering system different from that of the above-mentioned example.
本実施例ではスパッタ装置の構成が異なっても同様な効
果が得られることを示す。This example shows that similar effects can be obtained even if the configuration of the sputtering apparatus is different.
本実施例では、５インチＸ１５インチの直流（ＤＣ）プ
レナマグネトロン電極を有するスパッタ装置を用いＭｏ
膜を堆積した。使用装置では基板は一枚のサセプタ上に
搭載され、ターゲット上を一定速度で一方向に移動し、
基板の端から順にＭｏ膜が堆積されていく。In this example, a sputtering apparatus having a 5 inch x 15 inch direct current (DC) planar magnetron electrode was used.
A film was deposited. In the device used, the substrate is mounted on a single susceptor and moves over the target in one direction at a constant speed.
Mo films are deposited sequentially from the edge of the substrate.
約７Ｘ１０Ｐａ以下に真空排気したのち、スパッタガス
としてＮｅを導入し、スパッタ電流２Ａ、放電電圧２０
０Ｖ〜５００Ｖで膜厚１００ ｎｍ前後のＭｏ膜を堆積
した。After evacuation to about 7×10 Pa or less, Ne was introduced as sputtering gas, sputtering current was 2A, and discharge voltage was 20%.
A Mo film with a thickness of about 100 nm was deposited at 0V to 500V.
スパッタリングのガス圧を変えてＭｏ膜を堆積し、過酸
化水素水を用いたウェットエツチング法でエツチングし
て断面形状を調べると、実施例１と同様に０．４Ｐａの
低ガス圧で堆積したＭｏ膜はジャストエツチングでテー
パエツチング可能であるが、１Ｐａの高ガス圧で堆積し
たＭｏ膜は、垂直な断面を示すことが分かった。A Mo film was deposited by changing the sputtering gas pressure, and the cross-sectional shape was examined by wet etching using hydrogen peroxide. As in Example 1, the Mo film was deposited at a low gas pressure of 0.4 Pa. Although the film can be tapered by just etching, it was found that the Mo film deposited at a high gas pressure of 1 Pa exhibits a vertical cross section.
［実施例３］
実施例１で用いたスパッタ装置を用い、ＮｅにＡｒを混
合したスパッタガスでＭｏ膜を堆積した。[Example 3] Using the sputtering apparatus used in Example 1, a Mo film was deposited using a sputtering gas containing a mixture of Ne and Ar.
スパッタガス圧は約０．５Ｐａ一定とした。The sputtering gas pressure was kept constant at about 0.5 Pa.
混合比（Ｎｏ／（Ｎｅ＋Ａｒ））が７０％以上ではジャ
ストエツチング条件でテーパ加工ができるが、上記未満
ではテーパ加工できなかった。When the mixing ratio (No/(Ne+Ar)) is 70% or more, taper processing can be performed under just etching conditions, but when it is less than the above, taper processing cannot be performed.
この場合、Ａｒ以外のＸｓ、 Ｋｒ、 Ｈｅ、 Ｒｎ等
の不活性ガスをＮｅに混合しても、同様にテーパ加工を
行うことが可能であった。In this case, even if an inert gas other than Ar, such as Xs, Kr, He, or Rn, was mixed with Ne, it was possible to perform taper processing in the same way.
〈発明の効果〉
以上、実施例と共に詳しく述べたように、本発明に係る
モリブデンパタンの形成方法を用いれば、終了判定の容
易なジャストエツチング状態でも、テーパ加工ができる
ので、再現性良くテーパ加工が得られる効果がある。<Effects of the Invention> As described above in detail along with Examples, by using the method for forming a molybdenum pattern according to the present invention, taper processing can be performed even in a just etching state where it is easy to determine the end of etching, so taper processing can be performed with good reproducibility. There is an effect that can be obtained.
また、テーパ加工できているので、上層に形成した絶縁
膜の被覆不良を生じないと共に、さらに上部に形成した
配線の断線を生じない効果がある。Further, since the tapered structure is formed, there is an effect that not only does the insulating film formed on the upper layer not have poor coverage, but also the wiring formed on the upper layer does not become disconnected.
第１図は、本発明の実施例１に於けるスパッタガス圧Ｐ
とＭｏ膜の内部応力σの関係と、ジャストエツチング条
件のＭｏパタンの断面形状を示す図である。FIG. 1 shows the sputtering gas pressure P in Example 1 of the present invention.
FIG. 4 is a diagram showing the relationship between the internal stress σ of the Mo film and the cross-sectional shape of the Mo pattern under just etching conditions.
Claims (1)
するモリブデンパタンの形成方法において、 圧縮応力状態下にモリブデン膜を堆積した 後、過酸化水素水を用いて加工することを特徴とするモ
リブデンパタンの形成方法。 ２）請求項１記載のモリブデンパタンの形成方法におい
て、 スパッタ法で用いるスパッタガスとして、 ネオンを用いることを特徴とするモリブデンパタンの形
成方法。 ３）請求項１記載のモリブデンパタンの形成方法におい
て、 スパッタ法で用いるスパッタガスとして、 ネオンを主成分とする不活性ガスの混合ガスを用いるこ
とを特徴とするモリブデンパタンの形成方法。 ４）請求項１記載のモリブデンパタンの形成方法におい
て、 スパッタ法で用いるスパッタガスとして、 ネオンとアルゴンとの混合ガスを用いることを特徴とす
るモリブデンパタンの形成方法。 ５）請求項１〜４記載のモリブデンパタンの形成方法に
おいて、 スパッタ法のスパッタガス圧を１Ｐａ未満 のガス圧とすることを特徴とするモリブデンパタンの形
成方法。[Claims] 1) A method for forming a molybdenum pattern in which a molybdenum film deposited by sputtering is patterned, characterized in that the molybdenum film is deposited under compressive stress and then processed using hydrogen peroxide solution. A method for forming a molybdenum pattern. 2) The method for forming a molybdenum pattern according to claim 1, wherein neon is used as a sputtering gas used in the sputtering method. 3) The method for forming a molybdenum pattern according to claim 1, wherein a mixed gas of an inert gas containing neon as a main component is used as a sputtering gas in the sputtering method. 4) The method for forming a molybdenum pattern according to claim 1, wherein a mixed gas of neon and argon is used as a sputtering gas used in the sputtering method. 5) The method for forming a molybdenum pattern according to claims 1 to 4, wherein the sputtering gas pressure in the sputtering method is set to a gas pressure of less than 1 Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6436290A JPH03266426A (en) | 1990-03-16 | 1990-03-16 | Formation of molybdenum pattern |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6436290A JPH03266426A (en) | 1990-03-16 | 1990-03-16 | Formation of molybdenum pattern |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03266426A true JPH03266426A (en) | 1991-11-27 |
Family
ID=13256078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6436290A Pending JPH03266426A (en) | 1990-03-16 | 1990-03-16 | Formation of molybdenum pattern |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03266426A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19943521A1 (en) * | 1999-09-09 | 2001-04-05 | Dresden Ev Inst Festkoerper | Process for adjusting the defined flank angle comprises influencing the flank angle by producing or adjusting defined joint stresses in the layer to be structured whilst a metal or metal oxide layer is deposited |
| US6329300B1 (en) | 1999-07-29 | 2001-12-11 | Nec Corporation | Method for manufacturing conductive pattern layer by two-step wet etching process |
-
1990
- 1990-03-16 JP JP6436290A patent/JPH03266426A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6329300B1 (en) | 1999-07-29 | 2001-12-11 | Nec Corporation | Method for manufacturing conductive pattern layer by two-step wet etching process |
| DE19943521A1 (en) * | 1999-09-09 | 2001-04-05 | Dresden Ev Inst Festkoerper | Process for adjusting the defined flank angle comprises influencing the flank angle by producing or adjusting defined joint stresses in the layer to be structured whilst a metal or metal oxide layer is deposited |
| DE19943521C2 (en) * | 1999-09-09 | 2001-11-29 | Dresden Ev Inst Festkoerper | Method for setting defined flank angles when producing layer structures |
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