JPH0382127A - Selective formation of metallic film - Google Patents
Selective formation of metallic filmInfo
- Publication number
- JPH0382127A JPH0382127A JP21884889A JP21884889A JPH0382127A JP H0382127 A JPH0382127 A JP H0382127A JP 21884889 A JP21884889 A JP 21884889A JP 21884889 A JP21884889 A JP 21884889A JP H0382127 A JPH0382127 A JP H0382127A
- Authority
- JP
- Japan
- Prior art keywords
- film
- wiring
- mixed solution
- sulfuric acid
- hydrogen peroxide
- 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.)
- Granted
Links
- 230000015572 biosynthetic process Effects 0.000 title description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- -1 phosphate ester Chemical class 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 238000005530 etching Methods 0.000 abstract description 12
- 238000004380 ashing Methods 0.000 abstract description 7
- 238000004140 cleaning Methods 0.000 abstract description 7
- 150000002148 esters Chemical class 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract 2
- 231100000719 pollutant Toxicity 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 238000005137 deposition process Methods 0.000 abstract 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 abstract 1
- 229910052721 tungsten Inorganic materials 0.000 description 25
- 239000010937 tungsten Substances 0.000 description 25
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 24
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000000356 contaminant Substances 0.000 description 7
- 150000003014 phosphoric acid esters Chemical class 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910021341 titanium silicide Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010016803 Fluid overload Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Electrodes Of Semiconductors (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
Description
【発明の詳細な説明】 以下の順序に従って本発明を説明する。[Detailed description of the invention] The present invention will be described in the following order.
Ａ、産業上の利用分野
Ｂ６発明の概要
Ｃ９従来技術
り１発明が解決しようとする問題点［第２図］Ｅ１問題
点を解決するための手段
１０作用
Ｇ、実施例［第１図］
Ｈ１発明の効果
（Ａ、産業上の利用分野）
本発明は金属膜の選択的形成方法、特にフッ素系エツチ
ング液で洗浄するとフッ化物が残存してしまうようなア
ルミニウム、チタン、チタンシリサイドの如き配線上に
形成した絶縁膜の開口部にタングステン等の金属膜を選
択的に形成する金属膜の選択的形成方法に関する。A. Industrial field of application B6 Summary of the invention C9 Prior art 1 Problems to be solved by the invention [Figure 2] E1 Means for solving the problems 10 Effects G. Examples [Figure 1] H1 Effects of the Invention (A. Field of Industrial Application) The present invention provides a method for selectively forming a metal film, especially on interconnects such as aluminum, titanium, and titanium silicide, where fluoride remains after cleaning with a fluorine-based etching solution. The present invention relates to a method for selectively forming a metal film such as tungsten in an opening of an insulating film formed in the above.
（Ｂ、発明の概要）
本発明は、上記の金属膜の選択的形成方法において、
配線表面の自然酸化膜やレジスト残渣により金属膜の選
択的成長が阻害されることを防止するため、
金属膜の選択的成長前に、硫酸、過酸化水素水及びリン
酸エステルの混合溶液による洗浄を行うものである。(B. Summary of the Invention) The present invention, in the above-mentioned method for selectively forming a metal film, includes the following steps: Before selective growth, cleaning is performed using a mixed solution of sulfuric acid, hydrogen peroxide, and phosphoric acid ester.
（Ｃ，従来技術）
タングステン膜の選択的形成は、一般に、半導体基板の
表面に配線膜を形成した後Ｓｉ０ｇ膜を形成し、該５ｉ
Ｏ−膜をフォトエツチングすることにより配線膜の表面
を選択的に露出させて開口部を形成し、その後水素還元
法あるいはシリコン還元法等によりタングステン膜を上
記開口部に気相成長させるという方法で行なわれる。(C, Prior Art) Selective formation of a tungsten film is generally performed by forming a wiring film on the surface of a semiconductor substrate, then forming a Si0g film, and
This method involves selectively exposing the surface of the wiring film by photoetching the O- film to form an opening, and then vapor-growing a tungsten film into the opening using a hydrogen reduction method or a silicon reduction method. It is done.
（Ｄ、発明が解決しようとする問題点）［第２図］
ところで、タングステン膜を形成する場合に第２図（Ａ
）に示すようにタングステン膜７が異常成長したり、同
図（Ｂ）に示すようにタングステン膜６の成長が部分的
に阻害されたりするという問題があった。同図において
、１は半導体基板、２はフィールド絶縁膜、３はフィー
ルド絶縁膜２上に形成された例えば１％ＳＬ含有アルミ
ニウムからなる配線膜、４は眉間絶縁膜、５は該層間絶
縁膜４を選択的にエツチングすることにより形成された
スルーホール、６は配線膜３のスルーホール５に露出す
る部分の表面上に気相成長したタングステン膜、７はレ
ジストの汚染物８を核として異常成長したタングステン
膜、９は配線膜３表面に生じた自然酸化膜（八β２０３
）である。(D. Problem to be solved by the invention) [Fig. 2] By the way, when forming a tungsten film, Fig. 2 (A)
), the tungsten film 7 grows abnormally, and the growth of the tungsten film 6 is partially inhibited, as shown in FIG. In the figure, 1 is a semiconductor substrate, 2 is a field insulating film, 3 is a wiring film made of aluminum containing 1% SL formed on the field insulating film 2, 4 is an insulating film between the eyebrows, and 5 is an interlayer insulating film 4. 6 is a tungsten film grown in a vapor phase on the surface of the portion of the wiring film 3 exposed to the through hole 5; 7 is an abnormally grown tungsten film with resist contaminants 8 as nuclei; 9 is a natural oxide film (8β203) formed on the surface of the wiring film 3.
).
第２図（Ａ）に示すようにタングステンが異常成長する
のは絶縁膜４をフォトエツチングした後レジスト膜を除
去した状態ではナトリウムＮａ、鉄Ｆｅ、カーボンＣ等
が汚染物８として残り、それが還元法によりタングステ
ン膜６を成長させる際に活性水素を発生する源となり、
延いては還元反応を生ぜしめ、タングステンの異常成長
の核となるためである。As shown in FIG. 2(A), the abnormal growth of tungsten is caused by the fact that sodium Na, iron Fe, carbon C, etc. remain as contaminants 8 when the resist film is removed after photoetching the insulating film 4. It becomes a source of active hydrogen when growing the tungsten film 6 by the reduction method,
This is because it causes a reduction reaction and becomes the core of abnormal growth of tungsten.
また、配線膜４のスルーホール５の表面に露出した部分
に自然酸化膜９がある場合にはその自然酸化膜９上には
タングステンが成長しないので、第２図（Ｂ）に示すよ
うにタングステンの成長が部分的に妨げられるという現
象が生じるのである。Furthermore, if there is a natural oxide film 9 on the exposed surface of the through hole 5 of the wiring film 4, tungsten will not grow on the natural oxide film 9, so tungsten will grow as shown in FIG. 2(B). This results in a phenomenon in which the growth of the plant is partially hindered.
そこで、本願発明者は特願平１−３４７８３号で提案済
の技術、即ち硫酸過水ボイルにより半導体ウェハ表面を
洗浄するという技術を駆使することを試みた。しかし、
この技術はシリコン半導体基板の拡散層上にタングステ
ン膜を選択的に形成する場合における前処理にはきわめ
て有効であるが、アルミニウム等の配線膜上にタングス
テン膜を選択的に形成する場合には硫酸過水ボイルによ
って第２図（Ｃ）に示すように配線膜３がエツチングさ
れたり、反応熱によって配線膜３の表面に自然酸化膜（
八β２０．）９が厚く形成されたりするという問題があ
った。というのは、硫酸過水は過酸化水素Ｈ，Ｏ，が分
解して水Ｈ，Ｏが生じて−しまうことはある程度避は得
ない。そして、この水Ｈ，０がアルミニウム配線膜３の
表面部を酸化する。ところで、硫酸通水は酸化物に対す
る侵蝕作用を有するので、その配線膜３の表面部に生じ
た金属酸化物を除去する。従って、このようなプロセス
の繰返しによって硫酸過水が配線膜３をエツチングして
しまうのである。１０は硫酸過水ボイルによりエツチン
グされた部分である。Therefore, the inventor of the present application attempted to make full use of the technique proposed in Japanese Patent Application No. 1-34783, that is, the technique of cleaning the surface of a semiconductor wafer using a sulfuric acid/hydrogen boil. but,
This technique is extremely effective for pretreatment when selectively forming a tungsten film on the diffusion layer of a silicon semiconductor substrate, but when forming a tungsten film selectively on a wiring film such as aluminum, it is difficult to use sulfuric acid. As shown in FIG. 2(C), the wiring film 3 is etched due to overhydration boiling, and a natural oxide film (
Eight β20. ) 9 was formed thickly. This is because it is inevitable to some extent that hydrogen peroxide (H, O) will decompose in sulfuric acid/hydrogen peroxide to produce water (H, O). Then, this water H,0 oxidizes the surface portion of the aluminum wiring film 3. By the way, since the sulfuric acid water flow has a corrosive effect on oxides, metal oxides formed on the surface of the wiring film 3 are removed. Therefore, by repeating such a process, the wiring film 3 is etched by the sulfuric acid peroxide. 10 is a portion etched by sulfuric acid boiling.
このような問題は、下地となる配線膜３がアルミニウム
からなる場合に限らず、チタンからなる場合あるいはチ
タンシリサイドからなる場合等フッ素系エツチング液に
よりエツチングできない金属材料からなる場合一般に生
じた。Such problems occur not only when the underlying wiring film 3 is made of aluminum, but also when it is made of a metal material that cannot be etched with a fluorine-based etching solution, such as when it is made of titanium or titanium silicide.
本発明はこのような問題点を解決すべく為されたもので
あり、配線表面の自然酸化膜やレジストにより金属膜の
成長が阻害されることを防止することを目的とする。The present invention has been made to solve these problems, and its purpose is to prevent the growth of a metal film from being inhibited by a natural oxide film or resist on the surface of a wiring.
（Ｅ、問題点を解決するための手段）
本発明金属膜の選択的形成方法は上記問題点を解決する
ため、金属膜の選択的成長前に、硫酸、過酸化水素水及
びリン酸エステルの混合溶液による洗浄を行うことを特
徴とする特
（Ｆ、作用）
本発明金属膜の選択的形成方法によれば、洗浄する混合
溶液中にリン酸エステルが入っており、該リン酸エステ
ルが混合溶液中の過酸化水素Ｈ２０、の分解を抑制し水
Ｈ，Ｏの発生を阻む働きをする。従って、水ＨｉＯによ
って配線膜の表面が一旦酸化され、それが混合溶液中の
硫酸通水によってエツチングされるという現象が抑制さ
れる。従って、配線膜が上記混合溶液によって過剰にエ
ツチングされることを阻みつつ自然酸化膜やレジストに
よる汚染物を除去することができ、延いてはタングステ
ン膜の選択的成長を正常に行なわせることが可能になる
。(E. Means for Solving the Problems) In order to solve the above-mentioned problems, the method for selectively forming a metal film of the present invention uses sulfuric acid, hydrogen peroxide solution, and phosphate ester before the selective growth of the metal film. According to the method for selectively forming a metal film of the present invention, the mixed solution to be cleaned contains a phosphoric ester, and the phosphoric ester is mixed with a mixed solution. It works to suppress the decomposition of hydrogen peroxide H20 in the solution and prevent the generation of water H and O. Therefore, the phenomenon that the surface of the wiring film is once oxidized by water HiO and then etched by passing sulfuric acid in the mixed solution is suppressed. Therefore, contaminants caused by the natural oxide film and resist can be removed while preventing the wiring film from being excessively etched by the above-mentioned mixed solution, which in turn allows the selective growth of the tungsten film to occur normally. become.
（Ｇ、実施例）［第１図］
以下、本発明金属膜の選択的形成方法を図示実施例に従
って詳細に説明する。(G, Example) [FIG. 1] Hereinafter, the method for selectively forming a metal film of the present invention will be explained in detail according to the illustrated example.
第１図（Ａ）乃至（Ｅ）は本発明金属膜の選択的形成方
法の一つの実施例を工程順に示す断面図である。FIGS. 1A to 1E are cross-sectional views showing one embodiment of the method for selectively forming a metal film of the present invention in the order of steps.
（Ａ）半導体基板１表面上の絶縁膜２の表面に例えば１
％シリコン含有アルミニウムからなる配線膜３を形成し
た後、その表面上に層間絶縁膜４を形成し、その後該絶
縁膜４上にフォトレジスト膜１０を形成し、該フォトレ
ジスト膜１０を露光し、現像し、次いで後該レジスト膜
１０をマスクとして絶縁膜４をエツチングしてスルーホ
ール５を形成する。第１図（Ａ）はそのエツチング後の
状態を示し、１１．１１、・・・は還元法によりタング
ステン膜の選択的成長を行なう際に水素ラジウムを発生
し易くするナトリウムＮａ、鉄Ｆｅ、炭素Ｃ等の汚染物
である。(A) For example, on the surface of the insulating film 2 on the surface of the semiconductor substrate 1,
After forming a wiring film 3 made of aluminum containing % silicon, an interlayer insulating film 4 is formed on the surface thereof, a photoresist film 10 is formed on the insulating film 4, and the photoresist film 10 is exposed to light. After developing, the insulating film 4 is etched using the resist film 10 as a mask to form a through hole 5. Figure 1 (A) shows the state after etching, and 11.11,... are sodium Na, iron Fe, carbon which facilitate generation of hydrogen radium when selectively growing a tungsten film by reduction method. These are contaminants such as C.
（Ｂ）次に、同図（Ｂ）に示すように０２アツシングに
よりレジスト膜１０を除去する。このアッシングをして
も汚染物１１．１１、・・・は残存する。また、配線膜
３の開口部５に露出した部分の表面にアルミナＡｊ２．
０３からなる２００人程席上厚さの自然酸化膜９が生じ
る。(B) Next, as shown in the same figure (B), the resist film 10 is removed by 02 ashing. Even after this ashing, the contaminants 11, 11, . . . remain. Further, alumina Aj2.
A natural oxide film 9 consisting of 0.03 and having a thickness above the seats of about 200 people is formed.
尚、このアッシングは酸素ガス０２により行なっても良
いが、オゾン０３により行なっても良い。また、アッシ
ングを行なわないで次の工程（Ｃ）に移る方法も採り得
る。しかし、レジスト膜１０をより完全に除去するには
アッシングを行なった方が好ましいといえる。Note that this ashing may be performed using oxygen gas 02, but may also be performed using ozone 03. It is also possible to proceed to the next step (C) without performing ashing. However, in order to remove the resist film 10 more completely, it is preferable to perform ashing.
（Ｃ）次に同図（Ｃ）に示すように、硫酸過水にリン酸
エステルを加えた混合溶液１２に半導体基板１を浸漬す
ることにより汚染物１１．１１、・・を除去すると共に
自然酸化膜９を１００人程席上ツチングする。すると、
表面がポーラスの１００人程席上自然酸化膜９が残る。(C) Next, as shown in Figure (C), the semiconductor substrate 1 is immersed in a mixed solution 12 of sulfuric acid peroxide and phosphoric acid ester, thereby removing contaminants 11, 11, etc. Approximately 100 people covered the oxide film 9 at their seats. Then,
A natural oxide film 9 remains on the seats for about 100 people whose surface is porous.
自然酸化膜９を１００人程席上すのは、自然酸化膜９が
全くなくなりその後配線３が急速にエツチングされてし
まうことを確実に避けるためである。The reason why about 100 people sit on the natural oxide film 9 is to ensure that the natural oxide film 9 does not completely disappear and the wiring 3 is rapidly etched afterwards.
混合溶液１２は例えば硫酸Ｈ，Ｓｏ、が９０容量％、過
酸化水素Ｈ２Ｏ２が６容量％、リン酸エステルが４容量
％の組成比を有したものを用いると良い。そして、混合
溶液１２の温度は３０〜５０℃にする。ちなみに、この
混合溶液１２が２５℃のときにおけるアルミニウムに対
するエツチング速度が２５人／ ｍ ｉ ｎであり、ラ
イトエツチングも行なうことができる。具体的には、こ
のライトエツチングにより自然酸化膜９が除去されたり
表面部がポーラスな状態になる。尚、硫酸過水にリン酸
エステルを加えるのは、過酸化水素Ｈ２０，の分解によ
る水Ｈ，Ｏの発生を防止し、水Ｈ，Ｏによる配線膜３の
酸化、乙の酸化物に対する硫酸過水によるエツチングに
よる過剰エツチングを防止するためである。The mixed solution 12 preferably has a composition ratio of 90% by volume of sulfuric acid H, So, 6% by volume of hydrogen peroxide H2O2, and 4% by volume of phosphoric acid ester. Then, the temperature of the mixed solution 12 is set to 30 to 50°C. Incidentally, when this mixed solution 12 is at 25° C., the etching rate for aluminum is 25 people/min, and light etching can also be performed. Specifically, by this light etching, the natural oxide film 9 is removed and the surface becomes porous. In addition, adding phosphoric acid ester to sulfuric acid peroxide prevents the generation of water H and O due to the decomposition of hydrogen peroxide H20, and prevents the oxidation of the wiring film 3 by water H and O and the sulfuric acid peroxide against the oxide of B. This is to prevent excessive etching due to etching with water.
（Ｄ）次に、同図（Ｄ）に示すように、スパッタリング
（プラズマエツチングでもよい）によりアルミナＡβｇ
ｏｚからなるポーラスな自然酸化膜９を除去する。これ
により、配線膜３の表面が開口部５に露出する。この工
程は必ずしも必要ではないが、より完全なコンタクト性
を得るにはあった方が良い。(D) Next, as shown in the same figure (D), alumina Aβg
The porous natural oxide film 9 made of oz. As a result, the surface of the wiring film 3 is exposed to the opening 5. Although this step is not necessarily necessary, it is better to have it in order to obtain more perfect contact.
（Ｅ）その後、同図（Ｅ）に示すようにタングステン膜
６をＣＶＤにより選択的にする。このタングステン膜６
の選択的にはエンクローチメントの少ない条件で行なっ
ても良いし、そうでない条件Ｔ’ Ｆ ｆｌつでｔ、！
＋八 目仕帥Ｌ７１＋ぐ：ロ ；−二社１−ｐより行な
っても良いし、Ｈ２還元法により行なっても良いし、ま
た、両者を組み合せても良い。(E) Thereafter, the tungsten film 6 is selectively formed by CVD as shown in (E) of the same figure. This tungsten film 6
It may be selectively performed under the condition of less encroachment, or under the condition of less encroachment, t,!
+8 Mechanism L71+gu:b;-Two companies 1-p may be used, H2 reduction method may be used, or both may be combined.
このような金属膜の選択的形成方法によれば、タングス
テン膜の選択的の前に硫酸、過酸化水素水及びリン酸エ
ステルの混合溶液１２により洗浄するのでタングステン
膜の異常成長の核となる汚染物１１．１１、・・・を除
去することができると共に自然酸化膜９を略除去できる
のでタングステン膜６を正常に成長させ易い。特に、タ
ングステン膜６の成長前に僅かに残ったポーラスな薄い
自然酸化膜９をスパッタリング等により除去しておけば
より良好なコンタクト性を得てタングステン膜６を成長
させることができる。According to such a method for selectively forming a metal film, cleaning is performed with a mixed solution 12 of sulfuric acid, hydrogen peroxide, and phosphate ester before selectively forming a tungsten film, so that contamination, which is the core of abnormal growth of the tungsten film, is removed. Since the particles 11, 11, . . . can be removed and the natural oxide film 9 can be substantially removed, the tungsten film 6 can be easily grown normally. In particular, if the slightly remaining porous thin native oxide film 9 is removed by sputtering or the like before the tungsten film 6 is grown, the tungsten film 6 can be grown with better contact properties.
そして、洗浄用の混合溶液１２中にはリン酸エステルが
含まれ、このリン酸エステルが混合溶液１２の過酸化水
素Ｈ２Ｏ２の分解を抑制する。The cleaning mixed solution 12 contains a phosphoric ester, and this phosphoric ester suppresses the decomposition of hydrogen peroxide H2O2 in the mixed solution 12.
従って、水Ｈ２０が発生しにくくなり、水Ｈ２０による
配線膜３の酸化、酸化物の硫酸過水による侵蝕を抑制す
る。従って、配線膜３に対する混合溶液によりエツチン
グ性が抑制されるので、配線膜３が混合溶液１２により
過剰エツチングされて配線膜３のパターンが狂ってしま
う虞れはない。Therefore, water H20 is less likely to be generated, and oxidation of the wiring film 3 by water H20 and corrosion of oxides by sulfuric acid perhydrogen are suppressed. Therefore, since the etching property of the wiring film 3 is suppressed by the mixed solution, there is no risk that the wiring film 3 will be excessively etched by the mixed solution 12 and the pattern of the wiring film 3 will be distorted.
尚、本実施例においては配線膜３の材料がアルミニウム
であった。しかし、本発明は必ずしもそれに限定されず
、フッ素系エツチング液で処理するとフッ化物が残るよ
うな材料例えば、チタン、チタンシリサイドによって配
線膜が形成されている場合にも本発明を適用することが
できる。In this example, the material of the wiring film 3 was aluminum. However, the present invention is not necessarily limited thereto, and the present invention can also be applied to cases where the wiring film is formed of a material that leaves fluoride when treated with a fluorine-based etching solution, such as titanium or titanium silicide. .
（Ｈ，発明の効果）
以上に述べたように、本発明金属膜の選択的形成方法は
、基板表面の配線上の絶縁膜に開口部を形成した後、該
開口部を含む上記絶縁膜表面を硫酸、過酸化水素水及び
リン酸エステルの混合溶液で洗浄し、その後、金属膜を
上記開口部に選択的に成長させることを特徴とするもの
である。(H, Effect of the Invention) As described above, in the method for selectively forming a metal film of the present invention, after forming an opening in the insulating film on the wiring on the surface of the substrate, the surface of the insulating film including the opening is The method is characterized in that the metal film is washed with a mixed solution of sulfuric acid, hydrogen peroxide, and phosphoric acid ester, and then a metal film is selectively grown in the opening.
従って、本発明金属膜の選択的形成方法によれば、洗浄
する混合溶液中にリン酸エステルが入っており、該リン
酸エステルが配線膜に対するエツチングな抑制する。従
って、配線膜が上記混合溶液によって過剰にエツチング
されることを阻みつつ自然酸化膜やレジストによる汚染
物を除去することができ、延いてはタングステン膜の選
択的を正常に行なうことが可能になる。Therefore, according to the method for selectively forming a metal film of the present invention, a phosphoric acid ester is contained in the cleaning mixed solution, and the phosphoric acid ester suppresses etching of the wiring film. Therefore, contaminants caused by the natural oxide film and resist can be removed while preventing the wiring film from being excessively etched by the above-mentioned mixed solution, which in turn makes it possible to properly selectively etch the tungsten film. .
第１図（Ａ）乃至（Ｅ）は本発明金属膜の選択的形成方
法の一つの実施例を工程順に示す断面図、第２図（Ａ）
乃至（Ｃ）は発明が解決しようとする問題点を示す断面
図である。
符号の説明
１・・・基板、３・・・配線、
５・・・開口部、６・・・金属膜、
１２・・・混合溶液。
出 願 人1(A) to 1(E) are cross-sectional views showing one embodiment of the method for selectively forming a metal film of the present invention in the order of steps, and FIG. 2(A)
7(C) are cross-sectional views showing problems to be solved by the invention. Explanation of symbols 1... Substrate, 3... Wiring, 5... Opening, 6... Metal film, 12... Mixed solution. applicant
Claims (1)
、該開口部を含む上記絶縁膜表面を硫酸、過酸化水素水
及びリン酸エステルの混合溶液で洗浄し、 その後、金属膜を上記開口部に選択的に成長させる ことを特徴とする金属膜の選択的形成方法(1) After forming an opening in the insulating film on the wiring on the substrate surface, the surface of the insulating film including the opening is cleaned with a mixed solution of sulfuric acid, hydrogen peroxide, and phosphate ester, and then the metal film is A method for selectively forming a metal film, comprising selectively growing a metal film in the opening.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21884889A JP2841529B2 (en) | 1989-08-25 | 1989-08-25 | Selective metal film formation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21884889A JP2841529B2 (en) | 1989-08-25 | 1989-08-25 | Selective metal film formation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0382127A true JPH0382127A (en) | 1991-04-08 |
| JP2841529B2 JP2841529B2 (en) | 1998-12-24 |
Family
ID=16726288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21884889A Expired - Fee Related JP2841529B2 (en) | 1989-08-25 | 1989-08-25 | Selective metal film formation method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2841529B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0590417A (en) * | 1991-04-15 | 1993-04-09 | Samsung Electron Co Ltd | Method for forming multilayered interconnection of semiconductor element |
| KR19980023075A (en) * | 1996-09-25 | 1998-07-06 | 배순훈 | Wafer Etching Method |
| US6012469A (en) * | 1997-09-17 | 2000-01-11 | Micron Technology, Inc. | Etch residue clean |
-
1989
- 1989-08-25 JP JP21884889A patent/JP2841529B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0590417A (en) * | 1991-04-15 | 1993-04-09 | Samsung Electron Co Ltd | Method for forming multilayered interconnection of semiconductor element |
| KR19980023075A (en) * | 1996-09-25 | 1998-07-06 | 배순훈 | Wafer Etching Method |
| US6012469A (en) * | 1997-09-17 | 2000-01-11 | Micron Technology, Inc. | Etch residue clean |
| US6192899B1 (en) | 1997-09-17 | 2001-02-27 | Micron Technology, Inc. | Etch residue clean with aqueous HF/organic solution |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2841529B2 (en) | 1998-12-24 |
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