JPH02183252A - Formation of metallic film - Google Patents
Formation of metallic filmInfo
- Publication number
- JPH02183252A JPH02183252A JP1002990A JP299089A JPH02183252A JP H02183252 A JPH02183252 A JP H02183252A JP 1002990 A JP1002990 A JP 1002990A JP 299089 A JP299089 A JP 299089A JP H02183252 A JPH02183252 A JP H02183252A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- film
- tungsten
- semiconductor substrate
- metal
- 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
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 239000000758 substrate Substances 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000004065 semiconductor Substances 0.000 claims abstract description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 239000010937 tungsten Substances 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052786 argon Inorganic materials 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- TUVSHOWZKJNTDS-UHFFFAOYSA-D C(C(=O)[O-])(=O)[O-].[W+5].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].[W+5] Chemical compound C(C(=O)[O-])(=O)[O-].[W+5].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].[W+5] TUVSHOWZKJNTDS-UHFFFAOYSA-D 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten dioxide Inorganic materials O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Electrodes Of Semiconductors (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
この発明は、半導体等の基板上に金属膜を形成する方法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a method for forming a metal film on a substrate such as a semiconductor.
（従来の技術）
基板、特に半導体基板上に金属膜を形成するための方法
として、化学気相蒸着法（ＣＶＤ法）やスパッタ法等が
従来用いられている。(Prior Art) Chemical vapor deposition (CVD), sputtering, and the like have been conventionally used to form metal films on substrates, particularly semiconductor substrates.
ＣＶＤ法は、化学反応を利用して基板上に金属膜を気相
成長させる方法である。この方法には、比較的容易に厚
い膜を形成することが゛できる利点がある。The CVD method is a method of growing a metal film on a substrate in a vapor phase using a chemical reaction. This method has the advantage that a thick film can be formed relatively easily.
また、スパッタ法は、重荷電粒子をターゲツト材に照射
し、その衝撃でターゲツト材から飛び出した粒子を対向
する試料上に付着させる方法である。この方法によって
形成された膜は、基板に対する密着力が強い。The sputtering method is a method in which heavily charged particles are irradiated onto a target material, and the particles ejected from the target material due to the impact are deposited on an opposing sample. The film formed by this method has strong adhesion to the substrate.
（発明が解決しようとする課題）
しかしながら、ＣＶＤ法では下地である基板の材料によ
って膜の成長性が異なるため、基板の種類に応じて温度
、圧力等の条件を変える必要がある。従って、場合によ
っては、基板を高温にする必要が生じる。例えば、シリ
コンウェハの全表面にタングステン膜を形成する場合に
は、ウェハを７００℃前後の高温にしなければならない
。このような高温は、既に回路が形成された半導体基板
に対しては好ましいものではない。また、ＧａＡｓ。(Problems to be Solved by the Invention) However, in the CVD method, the growth properties of the film vary depending on the material of the underlying substrate, so it is necessary to change conditions such as temperature and pressure depending on the type of substrate. Therefore, in some cases, it may be necessary to heat the substrate to a high temperature. For example, when forming a tungsten film on the entire surface of a silicon wafer, the wafer must be heated to a high temperature of around 700°C. Such high temperatures are not preferable for semiconductor substrates on which circuits have already been formed. Also, GaAs.
ＩｎＰ ｓ ＺｎＳ等の化合物半導体基板に対しても、
そのような高温は好ましいものではない。For compound semiconductor substrates such as InP s ZnS,
Such high temperatures are not desirable.
また、スパッタ法は形成される膜の段差被覆性に劣り、
さらに膜形成中に発生する紫外線、軟Ｘ線、荷電粒子等
が半導体装置の特性に悪影響を与えることがある。In addition, the sputtering method has poor step coverage of the formed film,
Furthermore, ultraviolet rays, soft X-rays, charged particles, etc. generated during film formation may adversely affect the characteristics of the semiconductor device.
この発明は、上記事情に鑑み、基板、特に半導体基板上
に段差被覆性の良い金属膜を、比較的低温で、かつ半導
体装置の特性に悪影響を及ぼすことなく形成する方法を
提供することを目的とする。In view of the above circumstances, an object of the present invention is to provide a method for forming a metal film with good step coverage on a substrate, particularly a semiconductor substrate, at a relatively low temperature and without adversely affecting the characteristics of a semiconductor device. shall be.
［発明の構成］
（課題を解決するための手段）
この発明の金属膜形成方法は、液相において基板上に金
属酸化物を析出させる工程と、析出した金属酸化物を金
属に還元する工程とを有することを特徴とする。[Structure of the Invention] (Means for Solving the Problems) The metal film forming method of the present invention includes a step of depositing a metal oxide on a substrate in a liquid phase, and a step of reducing the deposited metal oxide to a metal. It is characterized by having the following.
液相中で基板上に金属酸化物を析出させる方法としでは
、例えば、基板上に析出させようとする金属の塩の溶液
を調製し、この溶液に基板を浸漬した後、溶液中で金属
を酸化して基板上に析出させることによって行なうこと
ができる。As a method for depositing metal oxides on a substrate in a liquid phase, for example, a solution of a salt of the metal to be deposited on the substrate is prepared, the substrate is immersed in this solution, and then the metal is deposited in the solution. This can be done by oxidizing and depositing on the substrate.
基板上に析出した金属酸化物を金属に還元する方法とし
ては、例えば、金属酸化物の層が形成された基板を水素
ガス雰囲気下で加熱°することにより行なうことができ
る。通常、金属酸化物の還元は気相で行なうが、液相に
おいて行なうこともできる。As a method for reducing the metal oxide deposited on the substrate to metal, it can be carried out, for example, by heating the substrate on which the metal oxide layer is formed in a hydrogen gas atmosphere. The reduction of metal oxides is usually carried out in the gas phase, but it can also be carried out in the liquid phase.
（作用）
液相中における基板上への金属酸化物の析出と、この金
属酸化物の高純度化および金属への還元は共に比較的低
温で行なうことができる。(Function) Both the precipitation of a metal oxide on a substrate in a liquid phase, the purification of this metal oxide, and its reduction to a metal can be performed at a relatively low temperature.
（実施例） 以下、この発明の実施例を図面を参照して説明する。(Example) Embodiments of the present invention will be described below with reference to the drawings.
まず、第１図に示すように反応容器３内のタングステン
（ｖ）オキザラト錯体［ＷＯ２（Ｃ２０４）］ −の水
溶液ｌを室温以下、好ましくは０〜１０℃に冷却し、タ
ングステン膜を形成しようとする半導体基板２を浸漬す
る。これを数時間もしくは数十時間静置することにより
第２図に示すように、半導体基板上に三酸化タングステ
ンＷ０３が析出し、三酸化タングステン膜（ＷＯ３膜）
４を形成する。タングステン（Ｖ）オキザラト錯体水溶
液１は、例えば、タングステン酸カルシウム塩に２ Ｗ
Ｏ４とシュウ酸Ｈ２Ｃ２０４との混合水溶液を、鉛を陰
極とし、飽和シュウ酸水溶液をアノード液として電解還
元することにより得ることができる。このようにして形
成されたタングステン（Ｖ）オキザラト錯体は、溶液中
の溶存酸素によって容易に三酸化タングステンＷＯ３に
酸化され、基板上に析出する。First, as shown in Fig. 1, an aqueous solution l of tungsten (v) oxalate complex [WO2(C204)] - in a reaction vessel 3 is cooled to below room temperature, preferably 0 to 10°C, to form a tungsten film. The semiconductor substrate 2 to be heated is immersed. By allowing this to stand for several hours or tens of hours, tungsten trioxide W03 is deposited on the semiconductor substrate as shown in Figure 2, forming a tungsten trioxide film (WO3 film).
form 4. Tungsten (V) oxalate complex aqueous solution 1 is, for example, 2 W
It can be obtained by electrolytically reducing a mixed aqueous solution of O4 and oxalic acid H2C204 using lead as a cathode and a saturated oxalic acid aqueous solution as an anode. The tungsten (V) oxalate complex thus formed is easily oxidized to tungsten trioxide WO3 by dissolved oxygen in the solution, and deposited on the substrate.
次いで、表面にｗＯ３膜４が形成された半導体基板２を
溶液１から取出し、アルゴン等の不活性ガス中において
約４００℃で熱処理して高純度化する。Next, the semiconductor substrate 2 with the wO3 film 4 formed on its surface is taken out from the solution 1 and heat treated at about 400° C. in an inert gas such as argon to achieve high purity.
次に、第３図に示すように、半導体基板２を反応管６に
入れ、水素ガス ５雰囲気下において約３００℃で三酸
化タングステンをタングステンに還元する。これにより
、第４図に示すように、半導体基板２上に ０．５μｍ
程度のタングステン膜７が形成される。Next, as shown in FIG. 3, the semiconductor substrate 2 is placed in a reaction tube 6, and the tungsten trioxide is reduced to tungsten at about 300° C. in an atmosphere of hydrogen gas. As a result, as shown in FIG.
A tungsten film 7 of about 100% is formed.
また、この発明の金属膜形成方法はタングステンのみな
らず、他の金属、例えばモリブデンに対しても同様に適
用することができる。Further, the metal film forming method of the present invention can be applied not only to tungsten but also to other metals, such as molybdenum.
さらに、この発明をデバイスに適用する場合は、高融点
金属の配線、ゲート電極ある′いはコンタクト電極等に
採用できる。基板は、ＳｉやＧａＡｓ等の半導体に限ら
ず、例えばガラス基板でも構わない。Furthermore, when the present invention is applied to a device, it can be used for high melting point metal wiring, gate electrodes, contact electrodes, etc. The substrate is not limited to a semiconductor such as Si or GaAs, and may be a glass substrate, for example.
ガラス基板を用いるものとしては、透明ガラス基板表面
に上記実施例の方法で金属膜を゛設けて、これをパター
ニングし、露光装置用のフォトマスクを作る場合などが
挙げられる。Examples of cases where a glass substrate is used include the case where a metal film is provided on the surface of a transparent glass substrate by the method described in the above embodiment, and this is patterned to make a photomask for an exposure device.
この発明の金属膜形成方法は、半導体基板に対して好適
に用いることができる。特に、既に回路が形成された半
導体基板、またはＧａＡｓ５ ＩｎＰ 。The metal film forming method of the present invention can be suitably used for semiconductor substrates. In particular, semiconductor substrates with already formed circuits, or GaAs5InP.
ＺｎＳ等の化合物半導体基板のように、高温加熱によっ
て悪影響を受ける半導体基板に好適に用いることができ
る。It can be suitably used for semiconductor substrates that are adversely affected by high temperature heating, such as compound semiconductor substrates such as ZnS.
［発明の効果コ
以上のように、この発明の金属膜形成方法は、液相にお
いて基板上に金属酸化物を析出させる際の湯度が室温以
下であり、基板上に形成された金属酸化物膜の高純度化
および還元の際の温度が３００〜４００℃であるため、
比較的低温で金属膜を形成することができ、基板、特に
半導体基板に悪影響を与えることが少ない。[Effects of the Invention] As described above, the metal film forming method of the present invention is characterized in that the temperature of the hot water used to deposit the metal oxide on the substrate in the liquid phase is below room temperature, and the metal oxide formed on the substrate is Since the temperature during membrane purification and reduction is 300 to 400°C,
A metal film can be formed at a relatively low temperature, and there is little adverse effect on substrates, especially semiconductor substrates.
また、この発明の金属膜形成方法では液相において基板
上に金属酸化物を析出堆積させて金属酸化物膜を形成さ
せる。このため、この金属酸化物膜は段差被覆性に優れ
ており、したがって、この金属酸化物膜を還元すること
により得られる金属膜も段差被覆性に優れている。Further, in the metal film forming method of the present invention, a metal oxide film is formed by precipitating and depositing a metal oxide on a substrate in a liquid phase. Therefore, this metal oxide film has excellent step coverage, and therefore, the metal film obtained by reducing this metal oxide film also has excellent step coverage.
第１図ないし第４図はこの発明の詳細な説明する図であ
る。
■・・・タングステン（Ｖ）オキザラト錯体水溶液、２
・・・半導体基板、３・・・反応容器、４・・・二酸化
タングステン膜、５・・・水素ガス、６・・・反応管、
タングステン膜。1 to 4 are diagrams explaining the invention in detail. ■...Tungsten (V) oxalato complex aqueous solution, 2
... Semiconductor substrate, 3... Reaction container, 4... Tungsten dioxide film, 5... Hydrogen gas, 6... Reaction tube,
tungsten film.
Claims (4)
程と、 析出した金属酸化物を金属に還元する工程とを有するこ
とを特徴とする金属膜の形成方法。(1) A method for forming a metal film, comprising the steps of depositing a metal oxide on a substrate in a liquid phase, and reducing the deposited metal oxide to a metal.
成方法。(2) The forming method according to claim 1, wherein the substrate is a semiconductor substrate.
形成方法。(3) The forming method according to claim 2, wherein the metal is tungsten.
成方法。(4) The forming method according to claim 2, wherein the metal is molybdenum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1002990A JPH02183252A (en) | 1989-01-10 | 1989-01-10 | Formation of metallic film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1002990A JPH02183252A (en) | 1989-01-10 | 1989-01-10 | Formation of metallic film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02183252A true JPH02183252A (en) | 1990-07-17 |
Family
ID=11544818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1002990A Pending JPH02183252A (en) | 1989-01-10 | 1989-01-10 | Formation of metallic film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02183252A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6294467B1 (en) | 1998-03-18 | 2001-09-25 | Nec Corporation | Process for forming fine wiring |
| CN112875836A (en) * | 2019-11-29 | 2021-06-01 | 中国科学院大连化学物理研究所 | Tungsten trioxide electrode with controllable oxygen vacancy distribution and preparation and application thereof |
-
1989
- 1989-01-10 JP JP1002990A patent/JPH02183252A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6294467B1 (en) | 1998-03-18 | 2001-09-25 | Nec Corporation | Process for forming fine wiring |
| CN112875836A (en) * | 2019-11-29 | 2021-06-01 | 中国科学院大连化学物理研究所 | Tungsten trioxide electrode with controllable oxygen vacancy distribution and preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0070751B1 (en) | Method for lpcvd co-deposition of metal and silicon to form metal silicide | |
| US6270571B1 (en) | Method for producing narrow wires comprising titanium oxide, and narrow wires and structures produced by the same method | |
| US4652463A (en) | Process for depositing a conductive oxide layer | |
| JP2814445B2 (en) | Selective low-temperature chemical vapor deposition of gold. | |
| JPH02183252A (en) | Formation of metallic film | |
| JP3228660B2 (en) | Method for producing high-purity metal material for semiconductor element formation | |
| JP3376420B2 (en) | Method for producing zinc oxide-based compound patterned film | |
| JPH025521A (en) | Manufacture of semiconductor device | |
| JPS59169129A (en) | Method for sputtering high-melting point metal or high-melting point metal silicide | |
| JPS63241185A (en) | Method for depositing thin metallic film | |
| JPS63151052A (en) | Formation of electrode wiring of semiconductor device | |
| SU1162352A1 (en) | Method of manufacturing film structures | |
| JPH0658889B2 (en) | Thin film formation method | |
| JPS582241A (en) | Manufacture of transparent patterned electrode | |
| JPS61203652A (en) | Manufacture of semiconductor device | |
| JPH0419912A (en) | Transparent conductive film | |
| JP2003257964A (en) | Method of forming metal oxide thin film | |
| JPH0420982B2 (en) | ||
| JP2000080495A (en) | Preparation of compound thin film by electro deposition and its compound thin film | |
| JPH0860350A (en) | Production of high-purity metallic material, production of sputtering target and formation of wiring net | |
| JPS6325949A (en) | Formation of metallic thin film | |
| JPH10317073A (en) | Wiring coating for forming semiconductor device and semiconductor package | |
| JPS59110775A (en) | Formation of metal film | |
| JPH107494A (en) | Formation of oxide thin film | |
| JPH04157727A (en) | Pattern formation method |